CN113800650A - Environment-friendly preparation for blue-green algae treatment and preparation method thereof - Google Patents
Environment-friendly preparation for blue-green algae treatment and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 241000192700 Cyanobacteria Species 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 44
- 241000195493 Cryptophyta Species 0.000 claims description 42
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 32
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 29
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 29
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 17
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 16
- 229920001661 Chitosan Polymers 0.000 claims description 16
- 229940074391 gallic acid Drugs 0.000 claims description 16
- 235000004515 gallic acid Nutrition 0.000 claims description 16
- 235000010413 sodium alginate Nutrition 0.000 claims description 16
- 239000000661 sodium alginate Substances 0.000 claims description 16
- 229940005550 sodium alginate Drugs 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 239000002775 capsule Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 241000894006 Bacteria Species 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003094 microcapsule Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 8
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009832 plasma treatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 230000001360 synchronised effect Effects 0.000 claims description 5
- 230000002353 algacidal effect Effects 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 238000012851 eutrophication Methods 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract description 3
- 241000863031 Lysobacter Species 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 241000192710 Microcystis aeruginosa Species 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229960004599 sodium borate Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000143060 Americamysis bahia Species 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 230000035755 proliferation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
Classifications
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses an environment-friendly preparation for blue-green algae treatment and a preparation method thereof, and relates to the technical field of environment protection. According to the environment-friendly preparation for blue-green algae treatment and the preparation method thereof, the number of blue-green algae in the water body can be effectively reduced, the eutrophication of the water body is reduced, the light transmittance of the water body is improved and a good treatment effect is achieved in a mode of combining biological, chemical and physical prevention and treatment modes.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to an environment-friendly preparation for blue algae treatment and a preparation method thereof.
Background
Blue-green algae is unicellular prokaryotic organism, called blue-green algae and cyanobacteria, and most of the blue-green algae have colloidal coats outside cell walls, and are called glutinous algae. Among all algae, the blue algae is the simplest and most original one, when the content of the blue algae in water is less, the blue algae is dispersed in water in an individual manner, if the blue algae meets the appropriate conditions of water temperature, eutrophication, organic phosphorus and the like, the blue algae can grow rapidly, the blue algae can generate a colony effect after developing to a certain degree, the blue algae is gathered and covered on the water surface in a green paint shape, the water bloom is called as water bloom, the concentration of dissolved oxygen in the water body is reduced through various ways, and therefore aquatic animals such as fishes and shrimps can die, and further the water environment and aquatic ecosystem are damaged.
At present, the treatment of the blue algae comprises a physical control method, a chemical control method and a biological control method, wherein the physical control method comprises the steps of collecting the blue algae in a water body by a power mechanical device, then moving the blue algae out of the water body, or crushing a blue algae group by an algae removal machine, controlling the proliferation of the quantity of the blue algae, or adsorbing by using activated carbon, aerating and increasing the oxygen, and the method generally has good effect on small-area emergency treatment and has better effect on large-area pollution; the chemical prevention and control method adopts a chemical algicide to inhibit the blue algae or kill the blue algae, but the blue algae is killed, and simultaneously, the water body is polluted, so that secondary pollution is easily caused; the biological control method mainly adopts measures of planting fast-growing aquatic plants, stocking aquatic animals, biological grids, artificial biological floating islands and the like, is green and environment-friendly, but is usually longer in treatment period.
Disclosure of Invention
Aiming at the problems, the invention aims to design and provide an environment-friendly preparation for blue-green algae treatment and a preparation method thereof, which can effectively reduce the number of blue-green algae in a water body, reduce water eutrophication, improve the light transmittance of the water body and achieve good treatment effect in a mode of combining biological, chemical and physical control modes.
The invention solves the technical problems by the following technical means:
the preparation is microcapsule particles, the microcapsule takes a compound of polyethylene glycol, sodium alginate and chitosan as a capsule shell, modified montmorillonite as a capsule core, and an algicidal bacterium layer is filled between the capsule core and the capsule shell.
The blue algae treatment agent disclosed by the invention combines biological, chemical and physical control modes, adopts a water-soluble material as a capsule skin, is scattered into a water area to be treated when in use, the capsule skin is molten when meeting water, and the chitosan and sodium alginate in the capsule skin can play a certain condensation role at the moment, so that dispersed blue algae are gathered to a certain degree, the subsequent treatment is facilitated, then the internal algae-dissolving bacteria are released, the enzyme capable of dissolving cellulose is released to digest the cell wall of blue algae cells, the whole blue algae cells are gradually dissolved, the blue algae are captured and gathered through the internal montmorillonite modification, and meanwhile, nitrogen, phosphorus and the like in the water body are removed through ion exchange, pore adsorption and other modes, so that the purposes of effectively reducing the content of the blue algae in the water body, reducing the eutrophication of the water body and improving the light transmittance of the water body are achieved.
Further, the modified montmorillonite is obtained by activating montmorillonite and then carrying out graft modification by using gallic acid and dopamine hydrochloride as modifiers.
According to the modified montmorillonite, the gallic acid and the dopamine hydrochloride are introduced to the montmorillonite to serve as active side chain structures, so that phenolic hydroxyl groups and amino groups are introduced to the natural montmorillonite, the effect of hydrogen bonds formed between the natural montmorillonite and water molecules can be increased by introducing the phenolic hydroxyl groups, the hydrophilicity of the montmorillonite is increased, long-chain molecules of the gallic acid can play a certain auxiliary flocculation role in the use process, in addition, the phenolic hydroxyl groups and the amino groups are introduced, so that the modified montmorillonite can mutually form a network-shaped adhesion structure in the use process, the effects of network adhesion and electrostatic adsorption can be better generated on blue-green algae in a water body, then the modified montmorillonite is coagulated to form large-particle alum flocs, then the large-particle alum flocs are settled, and the large-particle alum flocs can be favorably sucked and carried out by utilizing a silt boat and the like in the follow-up process.
In addition, as phenolic hydroxyl groups on the gallic acid are easy to oxidize and lose effects, the microcapsule form and the algicidal bacterium layer outside the modified montmorillonite can also protect the gallic acid, thereby ensuring the action effect.
Further, the mass ratio of the polyethylene glycol to the sodium alginate to the chitosan is (5-7) to 2: 1.
The invention also discloses a preparation method of the environment-friendly preparation for blue algae treatment, which comprises the following steps:
s1: respectively weighing polyethylene glycol, sodium alginate and chitosan, respectively preparing aqueous solutions, and uniformly mixing the aqueous solutions to obtain a wall material solution;
s2: weighing zymolytic bacteria, adding the zymolytic bacteria into deionized water, and stirring to prepare a zymolytic bacteria suspension;
s3: taking modified montmorillonite, stirring and dispersing uniformly in the zymolytic suspension, slowly dropwise adding the wall material solution under the stirring condition, completely homogenizing, and then putting the mixed solution in a refrigerator for freezing for 30 min;
s4: and performing synchronous ultrasonic emulsification and inclusion on the frozen mixed solution, and then drying and forming to obtain microcapsule particles, namely the environment-friendly preparation for treating the blue algae.
Further, the polyethylene glycol is prepared into a solution with the mass fraction of 10-15%, the sodium alginate is prepared into a solution with the mass fraction of 5-8%, and the chitosan is prepared into a solution with the mass fraction of 3-4%.
Further, in the present invention,
the preparation method of the modified montmorillonite comprises the following steps:
pretreatment: taking activated montmorillonite, stirring and adding the activated montmorillonite into brominated 1-butyl-3-methyl halogenated imidazole, magnetically stirring and dispersing, performing low-temperature plasma treatment, performing suction filtration after the treatment is finished, washing a filter cake with cold ether for three times, and freeze-drying;
grafting: dissolving dopamine hydrochloride in deionized water by stirring, adding a hydrochloric acid solution to adjust the pH value to 4-4.5 to obtain a dopamine hydrochloride solution, weighing pretreated montmorillonite, adding the montmorillonite into the dopamine hydrochloride solution, oscillating for 20-30min to obtain a suspension, adding sodium borate and sodium bicarbonate into N-methylpyrrolidone respectively, stirring for 20-30min, adding gallic acid, continuing stirring for 30min, adding the suspension, dropwise adding a glutaraldehyde solution, continuing stirring and reacting for 15-18h under the nitrogen atmosphere, performing suction filtration after the reaction is finished, washing the obtained filter cake with deionized water, and performing freeze drying to obtain modified montmorillonite.
Furthermore, during the low-temperature plasma treatment, helium is used as working gas, the pressure is 1.4kV, the vacuum degree is 7Pa, and the treatment time is 4-6 min. .
Further, the activation of the montmorillonite is specifically as follows: spraying 10 wt% sulfuric acid solution on montmorillonite, stirring, aging for 4 hr, rolling for 2 times, oven drying in rotary kiln, roasting for activation, and rapidly cooling to obtain activated montmorillonite.
Through sulfuric acid treatment and roasting, the impurity content in the montmorillonite can be improved and reduced, and meanwhile, the active functional group content on the modified montmorillonite can be increased, so that the subsequent grafting modification is facilitated.
The invention has the beneficial effects that:
1. the environment-friendly preparation for blue-green algae treatment disclosed by the invention can effectively reduce the number of blue-green algae in a water body, reduce the eutrophication of the water body, improve the light transmittance of the water body and achieve a good treatment effect in a mode of combining biological, chemical and physical prevention and treatment modes.
2. The environment-friendly preparation for blue algae treatment provided by the invention has the advantages that the raw materials are all natural substances, no heavy metal ions and the like are used, the environment is protected, and no secondary pollution is generated.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
the invention relates to an environment-friendly preparation for blue-green algae treatment, which is microcapsule particles, wherein the microcapsule particles take a compound of polyethylene glycol, sodium alginate and chitosan as a capsule shell, modified montmorillonite as a capsule core, and an algicidal bacterium layer is filled between the capsule core and the capsule shell, and specifically comprises the following components:
example one
Preparation of modified montmorillonite
And (3) activation: spraying 10 wt% sulfuric acid solution on montmorillonite, stirring, aging for 4 hr, rolling for 2 times, oven drying in rotary kiln at 100 deg.C for 2 hr, heating to 200 deg.C for 1 hr for activation, and rapidly cooling to obtain activated montmorillonite.
Pretreatment: taking activated montmorillonite, stirring and adding the activated montmorillonite into brominated 1-butyl-3-methyl halogenated imidazole with the mass 4 times that of the montmorillonite, magnetically stirring and dispersing, taking helium as working gas, carrying out low-temperature plasma treatment for 4min under the conditions that the pressure is 1.4kV and the vacuum degree is 7Pa, carrying out suction filtration after the treatment is finished, washing a filter cake for three times by using cold ether, and freeze-drying;
grafting: according to the solid-liquid ratio of dopamine hydrochloride to deionized water of 3:4g/ml, dopamine hydrochloride is taken and stirred to be dissolved in deionized water, 1mol/L hydrochloric acid solution is added to adjust the pH value to 4-4.5 to obtain dopamine hydrochloride solution, pretreated montmorillonite with the mass being 2 times that of dopamine hydrochloride is weighed and added into the dopamine hydrochloride solution to be oscillated for 25min to obtain suspension, sodium borate and sodium bicarbonate are respectively added into N-methyl pyrrolidone, after stirring for 20min, gallic acid, N-methyl pyrrolidone, sodium borate, sodium bicarbonate, dopamine hydrochloride and gallic acid are added in a mass ratio of 4:0.6:1:3:2, after stirring is continued for 30min, stirring and reacting is continued for 18h under the nitrogen atmosphere, after the reaction is completed, suction filtration is carried out, filter cakes are obtained, and then the filter cakes are washed clean by deionized water, and freeze drying is carried out to obtain the modified montmorillonite.
Preparation of the formulations
S1: respectively weighing polyethylene glycol, sodium alginate and chitosan according to the mass ratio of 7:2:1, respectively preparing to obtain a 15 wt% polyethylene glycol aqueous solution, an 8 wt% sodium alginate aqueous solution and a 3 wt% chitosan solution, and then uniformly mixing the aqueous solutions to obtain a wall material solution;
s2: weighing lysobacter, adding the lysobacter into deionized water with the mass 10 times that of the lysobacter, and stirring to prepare a lysobacter suspension;
s3: adding modified montmorillonite into the zymolytic bacteria suspension according to the solid-to-liquid ratio of 35g/L, stirring and dispersing uniformly, slowly dropwise adding the wall material solution under the stirring condition, and freezing the mixed solution in a refrigerator for 30min after homogenizing completely;
s4: and adding the frozen mixed solution into a sound insulation chamber of an ultrasonic cell crusher, performing synchronous ultrasonic emulsification and inclusion on the mixed solution, and then drying and forming at the temperature of 80 ℃ to obtain microcapsule particles, namely the environment-friendly preparation for blue algae treatment.
Example two
Preparation of modified montmorillonite
And (3) activation: spraying 10 wt% sulfuric acid solution on montmorillonite, stirring, aging for 4 hr, rolling for 2 times, oven drying in rotary kiln at 200 deg.C for 2 hr, heating to 300 deg.C, calcining for 0.5-1 hr for activation, and rapidly cooling to obtain activated montmorillonite
Pretreatment: taking activated montmorillonite, stirring and adding the activated montmorillonite into brominated 1-butyl-3-methyl halogenated imidazole with the mass 5 times that of the montmorillonite, magnetically stirring and dispersing, taking helium as working gas, carrying out low-temperature plasma treatment for 6min under the conditions that the pressure is 1.4kV and the vacuum degree is 7Pa, carrying out suction filtration after the treatment is finished, washing a filter cake with cold ether for three times, and freeze-drying the montmorillonite;
grafting: according to the solid-liquid ratio of dopamine hydrochloride to deionized water of 3:4g/ml, dopamine hydrochloride is taken and stirred to be dissolved in deionized water, 1mol/L hydrochloric acid solution is added to adjust the pH value to 4-4.5 to obtain dopamine hydrochloride solution, pretreated montmorillonite with the mass being 2 times that of dopamine hydrochloride is weighed and added into the dopamine hydrochloride solution to be oscillated for 30min to obtain suspension, sodium borate and sodium bicarbonate are respectively added into N-methyl pyrrolidone, after stirring for 25min, gallic acid, N-methyl pyrrolidone, sodium borate, sodium bicarbonate, dopamine hydrochloride and gallic acid are added, the mass ratio of the gallic acid to the dopamine hydrochloride solution is 4:0.6:0.8:2:2, after stirring for 30min, stirring and reacting for 15h under the nitrogen atmosphere, after the reaction is finished, suction filtration is carried out, filter cakes are obtained, and then the filter cakes are washed clean by deionized water, and freeze drying is carried out to obtain modified montmorillonite.
Preparation of the formulations
S1: respectively weighing polyethylene glycol, sodium alginate and chitosan according to the mass ratio of 6:2:1, respectively preparing to obtain a 12 wt% polyethylene glycol aqueous solution, a 5 wt% sodium alginate aqueous solution and a 4 wt% chitosan solution, and then uniformly mixing the aqueous solutions to obtain a wall material solution;
s2: weighing lysobacter, adding the lysobacter into deionized water with the mass 11 times that of the lysobacter, and stirring to prepare a lysobacter suspension;
s3: adding modified montmorillonite into the zymolytic bacteria suspension according to the solid-to-liquid ratio of 20g/L, stirring and dispersing uniformly, slowly dropwise adding the wall material solution under the stirring condition, and freezing the mixed solution in a refrigerator for 30min after homogenizing completely;
s4: adding the frozen mixed solution into a sound insulation chamber of an ultrasonic cell crusher, carrying out synchronous ultrasonic emulsification and inclusion on the mixed solution, and then drying and forming at the temperature of 80 ℃ to obtain microcapsule particles, namely the environment-friendly preparation for blue algae treatment
EXAMPLE III
Preparation of modified montmorillonite
And (3) activation: spraying 10 wt% sulfuric acid solution on montmorillonite, stirring, aging for 4 hr, rolling for 2 times, oven drying in rotary kiln at 250 deg.C for 1 hr, heating to 350 deg.C, calcining for 0.5 hr for activation, and rapidly cooling to obtain activated montmorillonite.
Pretreatment: taking activated montmorillonite, stirring and adding the activated montmorillonite into brominated 1-butyl-3-methyl halogenated imidazole with the mass 3 times that of natural montmorillonite, magnetically stirring and dispersing, taking helium as working gas, carrying out low-temperature plasma treatment for 5min under the conditions that the pressure is 1.4kV and the vacuum degree is 7Pa, carrying out suction filtration after the treatment is finished, washing a filter cake with cold ether for three times, and freeze-drying the montmorillonite;
grafting: according to the solid-liquid ratio of dopamine hydrochloride to deionized water of 3:5g/ml, dopamine hydrochloride is taken and stirred to be dissolved in deionized water, 1mol/L hydrochloric acid solution is added to adjust the pH value to 4-4.5 to obtain dopamine hydrochloride solution, pretreated montmorillonite with the mass being 2 times that of dopamine hydrochloride is weighed and added into the dopamine hydrochloride solution to be oscillated for 30min to obtain suspension, sodium borate and sodium bicarbonate are respectively added into N-methyl pyrrolidone, after stirring for 20min, gallic acid, N-methyl pyrrolidone, sodium borate, sodium bicarbonate, dopamine hydrochloride and gallic acid are added, the mass ratio of the gallic acid to the dopamine hydrochloride solution is 4:0.5:0.8:2:3, after stirring for 30min, stirring and reacting for 15h under the nitrogen atmosphere, after the reaction is finished, suction filtration is carried out, filter cakes are obtained, and then the filter cakes are washed clean by deionized water, and freeze drying is carried out to obtain modified montmorillonite.
Preparation of the formulations
S1: respectively weighing polyethylene glycol, sodium alginate and chitosan according to a mass ratio of 5:2:1, respectively preparing to obtain 10 wt% polyethylene glycol aqueous solution, 7 wt% sodium alginate aqueous solution and 4 wt% chitosan solution, and then uniformly mixing the aqueous solutions to obtain a wall material solution;
s2: weighing lysobacter, adding into deionized water with the mass 12 times that of the lysobacter, and stirring to prepare a lysobacter suspension;
s3: adding modified montmorillonite into the zymolytic bacteria suspension according to the solid-to-liquid ratio of 25g/L, stirring and dispersing uniformly, slowly dropwise adding the wall material solution under the stirring condition, and freezing the mixed solution in a refrigerator for 30min after homogenizing completely;
s4: and adding the frozen mixed solution into a sound insulation chamber of an ultrasonic cell crusher, performing synchronous ultrasonic emulsification and inclusion on the mixed solution, then timely feeding the emulsified solution into a drying unit, and drying and forming to obtain microcapsule particles, namely the environment-friendly preparation for blue algae treatment.
The environment-friendly preparation for blue algae treatment prepared in the first to third embodiments is used for treating a lake generating water blooms, the detection shows that before treatment, the amount of blue algae in raw water is 98.07 mu g/L, the total nitrogen content is 6.97mg/L, and the total phosphorus content is 0.23mg/L, 5L of lake water is taken, the environment-friendly preparation for blue algae treatment prepared in the first to third embodiments is respectively added according to the solid-to-liquid ratio of 5g/L, and after stirring treatment for 1d, secondary detection is carried out on indexes in a water body, and the detection results are shown in Table 1:
TABLE 1 indexes in water after treatment
| Item | Example one | Example two | EXAMPLE III |
| Blue algae amount/microgram/L | 6.9 | 7.2 | 6.5 |
| Total nitrogen content/mg/L | 1.96 | 1.97 | 2.01 |
| Total phosphorus content mg/L | 0.03 | 0.03 | 0.02 |
As can be seen from the data in Table 1, after the water body generating the water bloom is treated for 1d by adopting the environment-friendly medicament for treating the blue algae, the removal rate of the blue algae in the water body reaches over 90 percent, and the content of nitrogen and phosphorus in the water body is also greatly reduced.
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 environment-friendly preparation for blue-green algae treatment is characterized by being microcapsule particles, wherein the microcapsule takes a compound of polyethylene glycol, sodium alginate and chitosan as a capsule shell, modified montmorillonite as a capsule core, and an algicidal bacterium layer is filled between the capsule core and the capsule shell.
2. The environment-friendly preparation for treating blue-green algae according to claim 1, wherein the modified montmorillonite is obtained by activating montmorillonite and then carrying out graft modification by using gallic acid and dopamine hydrochloride as modifiers.
3. The environment-friendly preparation for treating blue-green algae according to claim 2, wherein the mass ratio of the polyethylene glycol, the sodium alginate and the chitosan is (5-7) to 2: 1.
4. The preparation method of the environment-friendly preparation for blue algae treatment according to any one of claims 1 to 3, wherein the preparation method comprises the following steps:
s1: respectively weighing polyethylene glycol, sodium alginate and chitosan, respectively preparing aqueous solutions, and uniformly mixing the aqueous solutions to obtain a wall material solution;
s2: weighing zymolytic bacteria, adding the zymolytic bacteria into deionized water, and stirring to prepare a zymolytic bacteria suspension;
s3: taking modified montmorillonite, stirring and dispersing uniformly in the zymolytic suspension, slowly dropwise adding the wall material solution under the stirring condition, completely homogenizing, and then putting the mixed solution in a refrigerator for freezing for 30 min;
s4: and performing synchronous ultrasonic emulsification and inclusion on the frozen mixed solution, and then drying and forming to obtain microcapsule particles, namely the environment-friendly preparation for treating the blue algae.
5. The method for preparing the environment-friendly preparation for blue-green algae treatment according to claim 4, wherein the polyethylene glycol is prepared into a solution with a mass fraction of 10-15%, the sodium alginate is prepared into a solution with a mass fraction of 5-8%, and the chitosan is prepared into a solution with a mass fraction of 3-4%.
6. The preparation method of the environment-friendly preparation for blue algae treatment according to claim 5, wherein the preparation method of the modified montmorillonite comprises the following steps:
pretreatment: taking activated montmorillonite, stirring and adding the activated montmorillonite into brominated 1-butyl-3-methyl halogenated imidazole, magnetically stirring and dispersing, performing low-temperature plasma treatment, performing suction filtration after the treatment is finished, washing a filter cake with cold ether for three times, and freeze-drying;
grafting: dissolving dopamine hydrochloride in deionized water by stirring, adding a hydrochloric acid solution to adjust the pH value to 4-4.5 to obtain a dopamine hydrochloride solution, weighing pretreated montmorillonite, adding the montmorillonite into the dopamine hydrochloride solution, oscillating for 20-30min to obtain a suspension, adding sodium borate and sodium bicarbonate into N-methylpyrrolidone respectively, stirring for 20-30min, adding gallic acid, continuing stirring for 30min, adding the suspension, dropwise adding a glutaraldehyde solution, continuing stirring and reacting for 15-18h under the nitrogen atmosphere, performing suction filtration after the reaction is finished, washing the obtained filter cake with deionized water, and performing freeze drying to obtain modified montmorillonite.
7. The method for preparing the environment-friendly preparation for blue algae treatment according to claim 6, wherein helium gas is used as working gas in the low-temperature plasma treatment, the pressure is 1.4kV, the vacuum degree is 7Pa, and the treatment time is 4-6 min.
8. The method for preparing the environment-friendly preparation for blue algae treatment according to claim 7, wherein the activation of the montmorillonite is specifically as follows: spraying 10 wt% sulfuric acid solution on montmorillonite, stirring, aging for 4 hr, rolling for 2 times, oven drying in rotary kiln, roasting for activation, and rapidly cooling to obtain activated montmorillonite.
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