CN106745569A - A kind of preparation method of composite magnetic algicide - Google Patents
A kind of preparation method of composite magnetic algicide Download PDFInfo
- Publication number
- CN106745569A CN106745569A CN201611263172.3A CN201611263172A CN106745569A CN 106745569 A CN106745569 A CN 106745569A CN 201611263172 A CN201611263172 A CN 201611263172A CN 106745569 A CN106745569 A CN 106745569A
- Authority
- CN
- China
- Prior art keywords
- necked flask
- bag filter
- algicide
- temperature
- under
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003619 algicide Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 229920001661 Chitosan Polymers 0.000 claims abstract description 17
- 239000004793 Polystyrene Substances 0.000 claims abstract description 17
- 229920002223 polystyrene Polymers 0.000 claims abstract description 17
- 125000002091 cationic group Chemical group 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000502 dialysis Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 6
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229960003511 macrogol Drugs 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 abstract description 36
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 3
- 230000009881 electrostatic interaction Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 1
- 235000005979 Citrus limon Nutrition 0.000 description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000003053 toxin Substances 0.000 description 4
- 231100000765 toxin Toxicity 0.000 description 4
- 108700012359 toxins Proteins 0.000 description 4
- 244000248349 Citrus limon Species 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000034994 death Effects 0.000 description 2
- 231100000517 death Toxicity 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010003497 Asphyxia Diseases 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000192700 Cyanobacteria Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005422 algal bloom Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 231100000405 induce cancer Toxicity 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
Classifications
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a kind of preparation method of composite magnetic algicide, belong to algicide preparing technical field.The present invention is first with citric acid-modified nano ferriferrous oxide, recycle glycidyltrimetiiylammonium ammonium chloride and chitosan reaction, prepare cationic chitosan, then with polystyrene emulsion as template, the ferroferric oxide nano granules of cationic chitosan and citric acid-modified are wrapped in template successively by electrostatic interaction, polystyrene kernel is removed finally by being dialysed in N, N dimethylformamides, the composite magnetic algicide with hollow-core construction is obtained.The composite magnetic algicide prepared in the present invention can make Measures of Algae in Water Body flocculate, and effective removal, alga-killing rate reaches more than 99.85%；Water body will not be polluted, after use, water body is limpid, colourless, meet the requirement of environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of composite magnetic algicide, belong to algicide preparing technical field.
Background technology
The lake of China more than 66%, reservoir are in eutrophication, and wherein weight eutrophy and super eutrophy accounts for 22%, from
And result in algal bloom phenomenon and frequently occur.The harm performance of algae is mainly：（1）The undue growth of algae, makes water in water
Body color changes, and landscape function is lost；（2）Substantial amounts of algae is overlying on the water surface, blocks the photosynthesis of plants in water, leads
Water body severe depletion of oxygen is caused, while the dead process consumption oxygen in water for decomposing of algae, makes the deaths by suffocation such as fish, it is serious broken
The ecological functions of bad water body；（3）The materials such as the ground depth and the different borneol of 2- methyl that are discharged during algal grown cause running water
Peculiar smell, has a strong impact on the mouthfeel of running water, while the Algae toxins of algae release cannot be removed by conventional water technology, and
Algae toxins may induce cancer, and the health hazard to user is very big；（4）Algae in raw water of waterworks can block filter tank,
Water factory's filter back washing frequency is caused to raise, so as to lift water producing cost, the algae that filter tank is penetrated on a small quantity can influence water supply quality.
Therefore, the algae how effectively gone in water removal is whole world questions of common interest.
More typical flocculant is that natural clay flocculation removes algae, can be combined and be formed with frustule using natural clay
Settling of floccus kills frustule or absorption nutritive salt or influences its photosynthesis in this process or directly to water bottom
Frustule is set to lose resistance to condition with growth etc. indirectly except algae.Natural clay mineral except algae cost, to environment and non-red tide or
The aspects such as wawter bloom biotic influence are better than other algae-removing methods, but because sol property is poor, the rapid ability for condensing, precipitating algae is low,
Need to largely broadcast sowing, administer algae pollution to large area and bring raw material and the excessive problem of sludge amount.Therefore the Chinese Academy of Sciences is ecological
Environmental Research Center State Key Laboratory of Environmental Aquatic Chemistry, RCEES and Qingdao University of Science and Technology's material and environmental science institute all enter respectively
Go the chitin modified influence that microcystic aeruginosa is removed to clay flocculating, and shitosan and natural clay mineral sepiolite are compounded
The research of microcystic aeruginosa in cohesion water body.Natural clay mineral has good suction-operated to microcystic aeruginosa, then compounds
Upper chitosan flocculant, by the adsorption bridging and electrical neutralization double action of shitosan, the further net of flco of formation catches water
Small flco in body, makes that the flco to be formed is thick, densification, and sinking speed is fast, and the water after treatment is limpid.Chinese Academy of Sciences's ion beam life
The experiment of thing engineering science emphasis had been developed in former patent and has been combined using shitosan and magnetic, and the magnetic flocculant being made can be with
Algae shape is flocculated to form magnetic flco, is easy to be removed using externally-applied magnetic field.But clay is except the main deficiency of algae：Simply by blue-green algae
The bottom is deposited to after absorption, the algae for dropping to the bottom still lives, still can survived and amount reproduction over a period to come；Its
Secondary, the algae for dropping to the bottom is in anaerobic condition, if after rotting, hydrogen sulfide gas and Algae toxins can be discharged, and Algae toxins
Cannot decompose, benthon and the biological destruction of being suffocated of spore can be caused after being spread in water body, serious causes bed mud
Anoxic, causes secondary pollution and biological death or even releases pernicious gas, and further destruction aqueous bio chain, cures the symptoms, not the disease.
Although shitosan can make algae flocculate and effectively removal with magnetic compound, it has the disadvantage that magnetic is combined not with shitosan
Jail, causes magnetic to depart from flco, and because magnetic density is excessive, is easily deposited on the bottom, is difficult by magnet absorption, and removal efficiency is received
To influence.
The content of the invention
The technical problems to be solved by the invention are：During traditional magnetic algicide use, magnetic easily with formation
Floccule body depart from, and because magnetic density is excessive, be easily deposited on the bottom, be difficult by magnet absorption, cause algae removal rate low
Problem, there is provided one kind using polystyrene emulsion be template, prepare the side of the composite magnetic algicide of hollow-core construction
Method.The present invention recycles glycidyltrimetiiylammonium ammonium chloride to gather with shell first with citric acid-modified nano ferriferrous oxide
Sugar reaction, prepares cationic chitosan, then with polystyrene emulsion as template, by electrostatic interaction by cation
The ferroferric oxide nano granules of shitosan and citric acid-modified are wrapped in template successively, finally by N, N- dimethyl methyls
Dialysed in acid amides and remove polystyrene kernel, obtain the composite magnetic algicide with hollow-core construction.The present invention utilizes hollow knot
Structure, reduces the density of algicide, and Measures of Algae in Water Body can be made to flocculate during use, and floats on water surface, not by water body depth
Degree influence, can remove algae by magnet absorption, and be firmly combined with, and efficiently solve traditional magnetic algicide algae removal rate low
Problem.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
（1）In the there-necked flask of belt stirrer, 3~5g nano ferriferrous oxides are sequentially added, 60~80mL mass fractions are
0.6~0.8% citric acid solution, then with 3~5mL/min speed to nitrogen is passed through in there-necked flask, under nitrogen guard mode,
8~12h is stirred with 200~300r/min rotating speeds, then material in there-necked flask is transferred to bag filter, and by bag filter be placed in from
Dialysed 3~5 days in sub- water, collect material in bag filter, be placed in baking oven, dried extremely under the conditions of being 105~110 DEG C in temperature
Constant weight, obtains modified Nano ferroso-ferric oxide, standby；
（2）100~150g shitosans are weighed successively, and 260~300g glycidyltrimetiiylammonium ammonium chlorides pour into belt stirrer
In there-necked flask, with 600~800r/min rotating speeds stirring 30~45min of mixing, under stirring, by dropping funel to three
It is 20% sodium hydroxide solution that 5~8mL mass fractions are added dropwise in mouth flask, and control is dripped off in 3~5min, treats completion of dropping, will
There-necked flask is moved in water-bath, in temperature be 75~80 DEG C, rotating speed be 300~500r/min under the conditions of, constant temperature stirring reaction 2
~4h, obtains cationic chitosan, standby；
（3）In the there-necked flask of belt stirrer, 200~300mL mass fractions are sequentially added for 45~50% Macrogol 4000s
Solution, 100~150mL absolute ethyl alcohols, 80~100mL deionized waters, 1~3g potassium peroxydisulfates, 120~180mL styrene, then will
There-necked flask is moved in water-bath, in temperature be 65~70 DEG C, rotating speed be 300~500r/min under the conditions of, constant temperature stirring reaction 6
~8h, obtains polystyrene emulsion；
（4）10~15g steps are taken successively（2）Standby cationic chitosan, the above-mentioned gained polystyrene emulsions of 300~500mL,
In entering beaker, then beaker is placed in digital display testing the speed in constant temperature blender with magnetic force, be 60~65 DEG C in temperature, rotating speed is 300~
Under the conditions of 400r/min, constant temperature 30~45min of stirring reaction adds 3~5g steps（1）The oxidation of standby modified Nano four three
Iron, continues 45~60min of constant temperature stirring reaction；
（5）Question response terminates, and material in above-mentioned beaker is poured into bag filter, then bag filter is placed in DMF
48~72h of dialysis, collects material in bag filter, and material in bag filter is placed in baking oven, in temperature be 75~80 DEG C of conditions
6~8h of lower drying, discharging, obtains final product composite magnetic algicide.
Application process of the invention：Composite magnetic algicide prepared by the present invention is spread into the water body of algae long, control is spread
The amount for entering is 25~35mg/L, after being sprinkled into 1~2 day, flco is removed into the water surface above water body with permanent magnet.Through inspection
Survey, after 1~2 day, water body is limpid, colourless, and alga-killing rate reaches more than 99.85%, and the regeneration of algae can be prevented in 5~7 months.
Compared with other method, Advantageous Effects are the present invention：
（1）The composite magnetic algicide prepared in the present invention can make Measures of Algae in Water Body flocculate, and effective removal, alga-killing rate reaches
More than 99.85%；
（2）Composite magnetic algicide prepared by the present invention will not be polluted to water body, limpid using rear water body, colourless, be met
The requirement of environmental protection.
Specific embodiment
First in the there-necked flask of belt stirrer, 3~5g nano ferriferrous oxides, 60~80mL mass point are sequentially added
Number is 0.6~0.8% citric acid solution, then with 3~5mL/min speed to nitrogen is passed through in there-necked flask, in nitrogen guard mode
Under, 8~12h is stirred with 200~300r/min rotating speeds, then material in there-necked flask is transferred to bag filter, and bag filter is placed in
Dialysed 3~5 days in deionized water, collect material in bag filter, be placed in baking oven, done under the conditions of being 105~110 DEG C in temperature
It is dry to obtain modified Nano ferroso-ferric oxide to constant weight, it is standby；100~150g shitosans, 260~300g glycidols are weighed successively
Base trimethyl ammonium chloride, pours into the there-necked flask of belt stirrer, with 600~800r/min rotating speeds stirring 30~45min of mixing,
Under stirring, by dropping funel to 5~8mL mass fractions are added dropwise in there-necked flask for 20% sodium hydroxide solution, control
Dripped off in 3~5min, treat completion of dropping, be 75~80 DEG C in temperature during there-necked flask moved into water-bath, rotating speed is 300
Under the conditions of~500r/min, constant temperature 2~4h of stirring reaction obtains cationic chitosan, standby；Again in the there-necked flask of belt stirrer
In, 200~300mL mass fractions are sequentially added for 45~50% Macrogol 4000 solution, 100~150mL absolute ethyl alcohols, 80
~100mL deionized waters, 1~3g potassium peroxydisulfates, 120~180mL styrene, then there-necked flask moved into water-bath, Yu Wen
It is 65~70 DEG C to spend, and rotating speed is under the conditions of 300~500r/min, constant temperature 6~8h of stirring reaction obtains polystyrene emulsion；Successively
The standby cationic chitosans of 10~15g are taken, the above-mentioned gained polystyrene emulsions of 300~500mL are poured into beaker, then by beaker
Digital display is placed in test the speed in constant temperature blender with magnetic force, in temperature be 60~65 DEG C, under the conditions of rotating speed is 300~400r/min, constant temperature
30~45min of stirring reaction, adds the standby modified Nano ferroso-ferric oxides of 3~5g, continue constant temperature stirring reaction 45~
60min；Question response terminates, and material in above-mentioned beaker is poured into bag filter, then bag filter is placed in DMF
48~72h of dialysis, collects material in bag filter, and material in bag filter is placed in baking oven, in temperature be 75~80 DEG C of conditions
6~8h of lower drying, discharging, obtains final product composite magnetic algicide.
Example 1
First in the there-necked flask of belt stirrer, 5g nano ferriferrous oxides are sequentially added, 80mL mass fractions are 0.8% lemon
Lemon acid solution, then with 5mL/min speed to nitrogen is passed through in there-necked flask, under nitrogen guard mode, with 300r/min rotating speeds
Stirring 12h, then material in there-necked flask is transferred to bag filter, and bag filter is placed in dialysis 5 days in deionized water, collect dialysis
Material in bag, is placed in baking oven, is dried to constant weight under the conditions of being 110 DEG C in temperature, obtains modified Nano ferroso-ferric oxide, standby
With；150g shitosans are weighed successively, and 300g glycidyltrimetiiylammonium ammonium chlorides are poured into the there-necked flask of belt stirrer, with
800r/min rotating speeds stirring mixing 45min, under stirring, is divided by dropping funel to 8mL mass is added dropwise in there-necked flask
Number is 20% sodium hydroxide solution, and control is dripped off in 5min, treats completion of dropping, during there-necked flask moved into water-bath, in temperature
It it is 80 DEG C, rotating speed is under the conditions of 500r/min, constant temperature stirring reaction 4h obtains cationic chitosan, standby；Again in belt stirrer
In there-necked flask, sequentially add 300mL mass fractions for 50% Macrogol 4000 solution, 150mL absolute ethyl alcohols, 100mL go from
Sub- water, 3g potassium peroxydisulfates, 180mL styrene, then there-necked flask is moved into water-bath, and in temperature it is 70 DEG C, rotating speed is 500r/
Under the conditions of min, constant temperature stirring reaction 8h obtains polystyrene emulsion；The standby cationic chitosans of 15g, the above-mentioned institutes of 500mL are taken successively
Polystyrene emulsion, pour into beaker, then beaker be placed in digital display and test the speed in constant temperature blender with magnetic force, in temperature be 65 DEG C,
Rotating speed continues permanent under the conditions of 400r/min, constant temperature stirring reaction 45min adds the standby modified Nano ferroso-ferric oxides of 5g
Warm stirring reaction 60min；Question response terminates, and material in above-mentioned beaker is poured into bag filter, then bag filter is placed in into N, N- diformazans
Dialyse 72h in base formamide, collects material in bag filter, and material in bag filter is placed in baking oven, in temperature be 80 DEG C of bars
8h is dried under part, is discharged, obtain final product composite magnetic algicide.
Composite magnetic algicide prepared by the present invention is sprinkled into the water surface of algae long, it is 35mg/L to control the amount being sprinkled into,
After being sprinkled into 2 days, flco is removed into the water surface above water body with permanent magnet.After testing, after 2 days, water body is limpid, nothing
Color, alga-killing rate reaches 99.95%, and the regeneration of algae can be prevented in 7 months.
Example 2
First in the there-necked flask of belt stirrer, 3g nano ferriferrous oxides are sequentially added, 60mL mass fractions are 0.6% lemon
Lemon acid solution, then with 3mL/min speed to nitrogen is passed through in there-necked flask, under nitrogen guard mode, with 200r/min rotating speeds
Stirring 8h, then material in there-necked flask is transferred to bag filter, and bag filter is placed in dialysis 3 days in deionized water, collect dialysis
Material in bag, is placed in baking oven, is dried to constant weight under the conditions of being 105 DEG C in temperature, obtains modified Nano ferroso-ferric oxide, standby
With；100g shitosans are weighed successively, and 260g glycidyltrimetiiylammonium ammonium chlorides are poured into the there-necked flask of belt stirrer, with
600r/min rotating speeds stirring mixing 30min, under stirring, is divided by dropping funel to 5mL mass is added dropwise in there-necked flask
Number is 20% sodium hydroxide solution, and control is dripped off in 3min, treats completion of dropping, during there-necked flask moved into water-bath, in temperature
It it is 75 DEG C, rotating speed is under the conditions of 300r/min, constant temperature stirring reaction 2h obtains cationic chitosan, standby；Again in belt stirrer
In there-necked flask, sequentially add 200mL mass fractions for 45% Macrogol 4000 solution, 100mL absolute ethyl alcohols, 80mL go from
Sub- water, 1g potassium peroxydisulfates, 120mL styrene, then there-necked flask is moved into water-bath, and in temperature it is 65 DEG C, rotating speed is 300r/
Under the conditions of min, constant temperature stirring reaction 6h obtains polystyrene emulsion；The standby cationic chitosans of 10g, the above-mentioned institutes of 300mL are taken successively
Polystyrene emulsion, pour into beaker, then beaker be placed in digital display and test the speed in constant temperature blender with magnetic force, in temperature be 60 DEG C,
Rotating speed continues permanent under the conditions of 300r/min, constant temperature stirring reaction 30min adds the standby modified Nano ferroso-ferric oxides of 3g
Warm stirring reaction 45min；Question response terminates, and material in above-mentioned beaker is poured into bag filter, then bag filter is placed in into N, N- diformazans
Dialyse 48h in base formamide, collects material in bag filter, and material in bag filter is placed in baking oven, in temperature be 75 DEG C of bars
6h is dried under part, is discharged, obtain final product composite magnetic algicide.
Composite magnetic algicide prepared by the present invention is sprinkled into the water surface of algae long, it is 25mg/L to control the amount being sprinkled into,
After being sprinkled into 1 day, flco is removed into the water surface above water body with permanent magnet.After testing, after 1 day, water body is limpid, nothing
Color, alga-killing rate reaches 99.92%, and the regeneration of algae can be prevented in 5 months.
Example 3
First in the there-necked flask of belt stirrer, 4g nano ferriferrous oxides are sequentially added, 70mL mass fractions are 0.7% lemon
Lemon acid solution, then with 4mL/min speed to nitrogen is passed through in there-necked flask, under nitrogen guard mode, with 250r/min rotating speeds
Stirring 10h, then material in there-necked flask is transferred to bag filter, and bag filter is placed in dialysis 4 days in deionized water, collect dialysis
Material in bag, is placed in baking oven, is dried to constant weight under the conditions of being 107 DEG C in temperature, obtains modified Nano ferroso-ferric oxide, standby
With；120g shitosans are weighed successively, and 270g glycidyltrimetiiylammonium ammonium chlorides are poured into the there-necked flask of belt stirrer, with
700r/min rotating speeds stirring mixing 40min, under stirring, is divided by dropping funel to 7mL mass is added dropwise in there-necked flask
Number is 20% sodium hydroxide solution, and control is dripped off in 4min, treats completion of dropping, during there-necked flask moved into water-bath, in temperature
It it is 77 DEG C, rotating speed is under the conditions of 400r/min, constant temperature stirring reaction 3h obtains cationic chitosan, standby；Again in belt stirrer
In there-necked flask, sequentially add 250mL mass fractions for 47% Macrogol 4000 solution, 120mL absolute ethyl alcohols, 90mL go from
Sub- water, 2g potassium peroxydisulfates, 150mL styrene, then there-necked flask is moved into water-bath, and in temperature it is 67 DEG C, rotating speed is 400r/
Under the conditions of min, constant temperature stirring reaction 7h obtains polystyrene emulsion；The standby cationic chitosans of 12g, the above-mentioned institutes of 400mL are taken successively
Polystyrene emulsion, pour into beaker, then beaker be placed in digital display and test the speed in constant temperature blender with magnetic force, in temperature be 62 DEG C,
Rotating speed continues permanent under the conditions of 350r/min, constant temperature stirring reaction 40min adds the standby modified Nano ferroso-ferric oxides of 4g
Warm stirring reaction 50min；Question response terminates, and material in above-mentioned beaker is poured into bag filter, then bag filter is placed in into N, N- diformazans
Dialyse 50h in base formamide, collects material in bag filter, and material in bag filter is placed in baking oven, in temperature be 77 DEG C of bars
7h is dried under part, is discharged, obtain final product composite magnetic algicide.
Composite magnetic algicide prepared by the present invention is sprinkled into the water surface of algae long, it is 30mg/L to control the amount being sprinkled into,
After being sprinkled into 2 days, flco is removed into the water surface above water body with permanent magnet.After testing, after 2 days, water body is limpid, nothing
Color, alga-killing rate reaches 99.89%, and the regeneration of algae can be prevented in 6 months.
Claims (1)
1. a kind of preparation method of composite magnetic algicide, it is characterised in that specific preparation process is：
（1）In the there-necked flask of belt stirrer, 3~5g nano ferriferrous oxides are sequentially added, 60~80mL mass fractions are
0.6~0.8% citric acid solution, then with 3~5mL/min speed to nitrogen is passed through in there-necked flask, under nitrogen guard mode,
8~12h is stirred with 200~300r/min rotating speeds, then material in there-necked flask is transferred to bag filter, and by bag filter be placed in from
Dialysed 3~5 days in sub- water, collect material in bag filter, be placed in baking oven, dried extremely under the conditions of being 105~110 DEG C in temperature
Constant weight, obtains modified Nano ferroso-ferric oxide, standby；
（2）100~150g shitosans are weighed successively, and 260~300g glycidyltrimetiiylammonium ammonium chlorides pour into belt stirrer
In there-necked flask, with 600~800r/min rotating speeds stirring 30~45min of mixing, under stirring, by dropping funel to three
It is 20% sodium hydroxide solution that 5~8mL mass fractions are added dropwise in mouth flask, and control is dripped off in 3~5min, treats completion of dropping, will
There-necked flask is moved in water-bath, in temperature be 75~80 DEG C, rotating speed be 300~500r/min under the conditions of, constant temperature stirring reaction 2
~4h, obtains cationic chitosan, standby；
（3）In the there-necked flask of belt stirrer, 200~300mL mass fractions are sequentially added for 45~50% Macrogol 4000s
Solution, 100~150mL absolute ethyl alcohols, 80~100mL deionized waters, 1~3g potassium peroxydisulfates, 120~180mL styrene, then will
There-necked flask is moved in water-bath, in temperature be 65~70 DEG C, rotating speed be 300~500r/min under the conditions of, constant temperature stirring reaction 6
~8h, obtains polystyrene emulsion；
（4）10~15g steps are taken successively（2）Standby cationic chitosan, the above-mentioned gained polystyrene emulsions of 300~500mL,
In entering beaker, then beaker is placed in digital display testing the speed in constant temperature blender with magnetic force, be 60~65 DEG C in temperature, rotating speed is 300~
Under the conditions of 400r/min, constant temperature 30~45min of stirring reaction adds 3~5g steps（1）The oxidation of standby modified Nano four three
Iron, continues 45~60min of constant temperature stirring reaction；
（5）Question response terminates, and material in above-mentioned beaker is poured into bag filter, then bag filter is placed in DMF
48~72h of dialysis, collects material in bag filter, and material in bag filter is placed in baking oven, in temperature be 75~80 DEG C of conditions
6~8h of lower drying, discharging, obtains final product composite magnetic algicide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611263172.3A CN106745569B (en) | 2016-12-30 | 2016-12-30 | Preparation method of composite magnetic algaecide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611263172.3A CN106745569B (en) | 2016-12-30 | 2016-12-30 | Preparation method of composite magnetic algaecide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106745569A true CN106745569A (en) | 2017-05-31 |
| CN106745569B CN106745569B (en) | 2020-08-11 |
Family
ID=58953402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611263172.3A Active CN106745569B (en) | 2016-12-30 | 2016-12-30 | Preparation method of composite magnetic algaecide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106745569B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075788A (en) * | 2019-05-23 | 2019-08-02 | 陕西科技大学 | A kind of cyanobacteria magnetic based on the modified preparation of sepiolite catches the preparation method of agent |
| CN111001396A (en) * | 2019-12-31 | 2020-04-14 | 西南石油大学 | Magnetic citric acid modified chitosan microsphere and preparation method and application thereof |
| CN111892133A (en) * | 2020-07-31 | 2020-11-06 | 江苏启创环境科技股份有限公司 | Biochemical tail water deep nitrogen and phosphorus removal method based on magnetic coagulation-adsorption coupling |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824611A (en) * | 2006-01-26 | 2006-08-30 | 中国科学院等离子体物理研究所 | Composite type inorganic polymer water quality purifier and method of magnetic gathering algae eliminating |
-
2016
- 2016-12-30 CN CN201611263172.3A patent/CN106745569B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824611A (en) * | 2006-01-26 | 2006-08-30 | 中国科学院等离子体物理研究所 | Composite type inorganic polymer water quality purifier and method of magnetic gathering algae eliminating |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075788A (en) * | 2019-05-23 | 2019-08-02 | 陕西科技大学 | A kind of cyanobacteria magnetic based on the modified preparation of sepiolite catches the preparation method of agent |
| CN111001396A (en) * | 2019-12-31 | 2020-04-14 | 西南石油大学 | Magnetic citric acid modified chitosan microsphere and preparation method and application thereof |
| CN111001396B (en) * | 2019-12-31 | 2022-02-22 | 西南石油大学 | Magnetic citric acid modified chitosan microsphere and preparation method and application thereof |
| CN111892133A (en) * | 2020-07-31 | 2020-11-06 | 江苏启创环境科技股份有限公司 | Biochemical tail water deep nitrogen and phosphorus removal method based on magnetic coagulation-adsorption coupling |
| CN111892133B (en) * | 2020-07-31 | 2021-12-14 | 江苏启创环境科技股份有限公司 | Biochemical tail water deep nitrogen and phosphorus removal method based on magnetic coagulation-adsorption coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106745569B (en) | 2020-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103754975B (en) | Water purifying agent and preparation method thereof | |
| KR101169563B1 (en) | An inorganic coagulant comprising waste plaster, starfish powder, shell powder and clay mineral | |
| CN105712599B (en) | A kind of landscape water body sediment repairing agent, method of preparation and use | |
| CN102674513B (en) | Composite medicinal preparation for biochemical effluent deep treatment of sewage plant | |
| CN104941574B (en) | A kind of inorganic ions modified zeolite composite and its application | |
| CN104276670A (en) | Sewage treating agent containing natural mineral substances and preparation method thereof | |
| CN108083560A (en) | A kind of rural activity area basin water resources recycle pollutant catabolic gene method and apparatus | |
| CN106745569A (en) | A kind of preparation method of composite magnetic algicide | |
| CN105906150A (en) | Sewage treatment system and technology for river ways in city | |
| CN205821003U (en) | A kind of river water cleaning device | |
| CN107243325A (en) | The preparation method of attapulgite mold toxin sorbent with antibacterial functions | |
| CN101306859A (en) | High-efficiency scavenging agent for water quality of aquaculture pond | |
| CN104891619A (en) | Algaecide for flocculating and settling alga bodies and preparation method of algaecide | |
| CN105329956A (en) | Sewage cleanser and preparation method thereof | |
| CN106186352A (en) | A kind of method utilizing porous cellulose aeroge immobilized microorganism bacterium to process ammonia nitrogen waste water | |
| CN104445453A (en) | Blue algae treating agent containing alfalfa roots and preparation method thereof | |
| CN102674517A (en) | Method for rapidly flocculating blue-green algae in water body | |
| CN205575878U (en) | Unpowered treatment facility of rural domestic sewage | |
| CN107986412A (en) | A kind of modification clay systems administered for breeding water body harmful algal bloom | |
| CN101381142B (en) | Blue algae scavenger using mineral material as carrier and preparation method thereof | |
| CN101647422A (en) | Composition for improving pond substrate and preparation method thereof | |
| CN106621561A (en) | Sewage filter screen for adsorbing nitrogen and phosphorus elements in sewage | |
| CN106732469A (en) | A kind of preparation method of magnetic absorption dephosphorization agent and its renovation process of product | |
| CN107382025B (en) | Pig farm sewage treatment filler, multi-element coupling process and system | |
| CN109987716A (en) | A kind of ecological green ditch host material of preventing and controlling agricultural area source pollution and the construction method of ecological green ditch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200717 Address after: 322100 Zhejiang, Jinhua, Dongyang, Jiangbei street, 1 New Village Applicant after: DONGYANG TEYI NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 213187, Jiangsu, Changzhou City Bell Tower District Five Star Street soup home village village 75 Applicant before: Lei Xiaotian |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |