CN116573708B - Blue algae scavenger and preparation method thereof - Google Patents
Blue algae scavenger and preparation method thereof Download PDFInfo
- Publication number
- CN116573708B CN116573708B CN202310564377.9A CN202310564377A CN116573708B CN 116573708 B CN116573708 B CN 116573708B CN 202310564377 A CN202310564377 A CN 202310564377A CN 116573708 B CN116573708 B CN 116573708B
- Authority
- CN
- China
- Prior art keywords
- fiber membrane
- hours
- blue algae
- solution
- titanium dioxide
- 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.)
- Active
Links
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 84
- 239000002516 radical scavenger Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 113
- 239000012528 membrane Substances 0.000 claims abstract description 87
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims description 69
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 53
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 23
- 239000010410 layer Substances 0.000 abstract description 13
- 239000012792 core layer Substances 0.000 abstract description 12
- 238000007539 photo-oxidation reaction Methods 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000002779 inactivation Effects 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 3
- 150000001412 amines Chemical group 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- -1 boron ions Chemical class 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 4
- 241000192700 Cyanobacteria Species 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 241000192710 Microcystis aeruginosa Species 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003053 toxin Substances 0.000 description 2
- 231100000765 toxin Toxicity 0.000 description 2
- 108700012359 toxins Proteins 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C02F1/28—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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
- D04H1/43828—Composite fibres sheath-core
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
- D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a blue algae scavenger and a preparation method thereof, and relates to the field of water pollution treatment. According to the preparation method, polyacrylonitrile is used as a core layer, tetrabutyl titanate and polyvinylpyrrolidone are used as shell layers, after a fiber membrane is prepared through coaxial electrostatic spinning, a modified silicon dioxide fiber membrane is prepared through first high-temperature treatment and second high-temperature treatment, and the blue algae removal effect of the blue algae scavenger is achieved by reducing the quantity of blue algae through the photooxidation effect of titanium dioxide and the adsorption effect of a fiber network structure; and then, the modified titanium dioxide fiber film sequentially reacts with N, N-diethyl-3- (trimethoxy silane) propylamine and 1, 4-butane sultone to form a mesoporous silica coating layer with a quaternary amine structure and a sulfonic group, so that the adsorption and inactivation effects of the scavenger on blue algae are further improved. The scavenger prepared by the invention has blue algae removal effect.
Description
Technical Field
The invention relates to the field of water pollution treatment, in particular to a blue algae scavenger and a preparation method thereof.
Background
Blue algae are algae organisms, also known as blue-green algae. Among all algae, cyanobacteria is the simplest, most primitive one. The phenomenon that the ecological balance is destroyed due to the mass propagation of blue algae caused by extremely severe water resource environment is called as blue algae bloom. Blue algae bloom can cause death of fish and shrimp, cause water pollution and have serious influence on production and life of human beings. In addition, cyanobacteria toxins can also seriously jeopardize human health. The toxic death of fish livestock and humans due to algae toxins has been reported in the united states, japan, australia, brazil, etc. The existing blue algae treatment methods are divided into physical, chemical, biological and other methods, but each method has respective advantages and disadvantages, and cannot be widely applied.
The chemical method is to remove algae by using algicides, is simple and easy to implement, has no influence on the landscape of the lake surface, but can cause secondary pollution, is unfavorable for the use of drinking water, can raise the lake bed, accelerates the ageing and swamp of the lake, and is not a suitable and effective removal method. The physical method is to drag out blue algae or centrifugation from water by a floatation method, so that the blue algae or centrifugation can treat both symptoms and root causes, has no adverse effect on water quality and aquatic organism population, has no secondary pollution, and can carry pollutants in water, but the method has high cost, is not suitable for large-area application, and needs to be continuously cleaned for a long time; in addition, the method has a certain influence on the landscape of the lake surface. The biological method can greatly reduce pollutants in water, keep the water clean within a certain time, has no influence on the landscape of the lake surface, has long time and insignificant effect, and cannot fundamentally remove the pollutants in the lake; the method has certain influence on the biological population structure and the biological diversity of the lake; dead algae can produce secondary pollution as a new pollution source, and the lake bed is lifted to accelerate ageing of the lake and swamp. The occurrence frequency of blue algae bloom in a plurality of lake water bodies in China is high, the algae biomass is huge, and the toxicity is strong, so that a method for preventing and controlling the blue algae bloom with long-acting, economical and safe is urgently needed.
Disclosure of Invention
The invention aims to provide a blue algae scavenger and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a blue algae scavenger and a preparation method thereof are provided, wherein the blue algae scavenger is prepared by sequentially carrying out a first high temperature treatment, a second high temperature treatment, a first dipping treatment and a second dipping treatment on a fiber film.
Further, the fiber membrane is prepared by coaxial electrostatic spinning of a polyacrylonitrile core spinning solution and a tetrabutyl titanate/polyvinylpyrrolidone shell spinning solution.
Further, the first high temperature treatment is as follows: the fiber membrane is treated for a period of time at 500-700 ℃ to obtain a titanium dioxide fiber membrane; the second high temperature treatment is as follows: and (3) after spraying the metal ion solution on the titanium dioxide fiber membrane, treating for a period of time at 400-500 ℃ to obtain the modified titanium dioxide fiber membrane.
Further, the second impregnation treatment is as follows: the first dipping treatment is as follows: immersing the modified titanium dioxide fiber membrane in an N, N-diethyl-3- (trimethoxy silane) propylamine solution for a period of time to obtain a silicon dioxide coating membrane; the second impregnation treatment is as follows: and immersing the silicon dioxide coating film in a 1, 4-butane sultone solution for a period of time to obtain the blue algae scavenger.
Further, the preparation method of the blue algae scavenger comprises the following preparation steps:
(1) Respectively injecting the shell spinning solution and the core spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.2-1.0 mm, the flow rate of the inner tube spinning solution is 0.5-1.5 mL/h, the diameter of the outer tube is 1-2 mm, the flow rate of the outer tube spinning solution is 0.5-1.5 mL/h, the voltage is 10-30 kV and the receiving distance is 10-30 cm to obtain a fiber membrane;
(2) Heating to 500-700 ℃ at a speed of 1-3 ℃/min, calcining the fiber membrane at a high temperature for 1-2 hours, cooling to 400-500 ℃, spraying a metal ion solution with a mass of 0.1-0.2 of the fiber membrane to the fiber membrane, and continuously reacting for 1-2 hours at a mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water of 11:6:1:1000-19:8:9:1000 to obtain a modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber film in an N, N-diethyl-3- (trimethoxysilyl) propylamine solution with the mass of 50-100 times that of the modified titanium dioxide fiber film, immersing for 1-3 hours at 100-200 rpm, washing for 3-5 times with methylene chloride, and vacuum drying for 2-3 hours at 40-50 ℃ under the vacuum degree of-0.08 MPa to obtain a silicon dioxide coating film;
(4) Immersing the silicon dioxide coating film in a 1, 4-butane sultone solution with the mass of 50-100 times that of the silicon dioxide coating film, wherein the mass ratio of 1, 4-butane sultone to tetrahydrofuran in the 1, 4-butane sultone solution is 0.1:100-0.2:100, reacting for 7-9 hours at the temperature of 40-50 ℃ at 200-300 rpm, washing for 3-5 times by using tetrahydrofuran, and vacuum drying for 2-3 hours at the temperature of 40-50 ℃ at the vacuum degree of-0.08 MPa to obtain the blue algae scavenger.
Further, the preparation method of the shell spinning solution in the step (1) comprises the following steps: mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11:5:0.8-12:7:0.8, stirring for 24 hours at 200-300 rpm, and standing for 12 hours to obtain a shell spinning solution.
Further, the preparation method of the core spinning solution in the step (1) comprises the following steps: mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 6:73-8:73, stirring for 2 hours at 200-300 rpm and a temperature of 55-65 ℃, and standing for 12 hours to obtain the core spinning solution.
Further, the solution of N, N-diethyl-3- (trimethoxysilyl) propylamine in the step (3) is prepared by mixing N, N-diethyl-3- (trimethoxysilyl) propylamine and methylene dichloride according to a mass ratio of 0.4:100-0.6:100.
Compared with the prior art, the invention has the following beneficial effects:
the blue algae scavenger is prepared by sequentially carrying out first high-temperature treatment, second high-temperature treatment, first impregnation and second impregnation treatment on a fiber membrane, wherein the fiber membrane is prepared by coaxially and electrostatically spinning a polyacrylonitrile core spinning solution and a tetrabutyl titanate/polyvinylpyrrolidone shell spinning solution, and has a blue algae removal effect.
Firstly, polyacrylonitrile is used as a core layer spinning solution, tetrabutyl titanate and polyvinylpyrrolidone are used as a shell layer spinning solution, a fiber membrane is prepared through coaxial electrostatic spinning, then a titanium dioxide fiber membrane is prepared through first high-temperature treatment, under the action of high temperature, the complete decomposition of polyvinylpyrrolidone and the decomposition and crystallization of tetrabutyl titanate form a shell layer with a mesoporous titanium dioxide structure, the polyacrylonitrile is carbonized and releases water and hydrogen to form a multi-structure, and simultaneously, through holes are formed with the shell layer under the action of overflow force of water and hydrogen, the photooxidation inactivation effect of titanium dioxide and the adsorption effect of the fiber membrane can reduce the blue algae quantity in a water body, so that a scavenger has the blue algae removal effect, the contact area of the membrane and the blue algae is increased through the porous structure of the fiber, the adsorption effect of the fiber membrane on the blue algae can be further improved, and the blue algae removal effect is increased; then carrying out a second high-temperature treatment, spraying boric acid, silver nitrate and cobalt nitrate on the titanium dioxide fiber film at a high temperature to prepare a modified titanium dioxide fiber film, doping boron ions, silver ions and cobalt ions into titanium dioxide under the action of the high temperature, forming an electron transmission channel by the silver ions, forming surface defects and doping energy levels by the cobalt ions and the boron ions, expanding the photoresponse range of the titanium dioxide, enhancing the photooxidation capability, simultaneously acting boric acid on the carbon cores of the fibers to enable the fibers to be actively carbonized, enhancing the photooxidation inactivation effect and adsorption effect of the fiber film on blue algae, and enhancing the blue algae removal effect.
Secondly, performing first impregnation treatment, reacting a silica group in N, N-diethyl-3- (trimethoxy silane) propylamine with a hydroxyl group on the surface of a fiber film, and performing self-polymerization to form a mesoporous silica film on the surface of the fiber, so that the specific surface area of the fiber film is further increased, and pollution of blue algae to titanium dioxide is prevented to influence photooxidation effect; then carrying out a second soaking treatment, wherein 1, 4-butane sultone is subjected to ring opening to form carboxyl and sulfonic acid groups, the carboxyl reacts with amino in N, N-diethyl-3- (trimethoxy silane) propylamine to form a quaternary ammonium structure, the quaternary ammonium structure can be electrically neutralized with algae cells to cause unbalance and condensation of the algae cells, and the sulfonic acid groups can increase the permeability of blue algae cell membranes and cell walls, so that the blue algae cell membranes and cell walls are easier to damage and inactivate, and the algae removal effect of the blue algae scavenger is further improved; in addition, the blue algae scavenger prepared by the invention is of a large-plane fiber membranous structure, and has good recoverability so as to prevent secondary pollution of the blue algae scavenger to the environment.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the methods for testing the indexes of the blue algae scavenger prepared in the following examples are as follows:
blue algae removal effect: the blue algae removal effect test is carried out by selecting a blue algae bloom typical algae species microcystis aeruginosa, adding the example and the comparative example with the same quality into the water body to be treated, wherein the mass ratio of the example to the comparative example to the water body to be treated is 1:10, and the microcystis aeruginosa in the water body to be treated is in the logarithmic growth phase, and the quantity is 10 7 Each per milliliter, atIlluminance of light isAfter 24 hours of irradiation at 8000 nits, the number of algal cells was measured by a hemocytometer method, and the algae removal rate was calculated using the following formula:
algae removal rate= (1-cell number before algae removal/cell number after algae removal) ×100%.
Example 1
(1) Mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11:5:0.8, stirring for 24 hours at 200rpm, and standing for 12 hours to obtain a shell spinning solution; mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 6:73, stirring for 2 hours at 200rpm and 55 ℃, and standing for 12 hours to obtain a core spinning solution; respectively injecting the shell layer spinning solution and the core layer spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.2mm, the flow rate of the inner tube spinning solution is 0.5mL/h, the diameter of the outer tube is 1mm, the flow rate of the outer tube spinning solution is 0.5mL/h, the voltage is 10kV and the receiving distance is 10cm to obtain a fiber membrane;
(2) Heating to 500 ℃ at a speed of 1 ℃/min, calcining the fiber membrane at a high temperature for 1h, cooling to 400 ℃, spraying a metal ion solution with the mass of 0.1 of the fiber membrane to the fiber membrane, and continuously reacting for 1h at a mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water of 11:6:1:1000 in the metal ion solution to obtain a modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber film in an N, N-diethyl-3- (trimethoxysilyl) propylamine solution with the mass ratio of 50 times of that of the modified titanium dioxide fiber film, namely, the N, N-diethyl-3- (trimethoxysilyl) propylamine solution, namely, the mass ratio of N, N-diethyl-3- (trimethoxysilyl) propylamine to dichloromethane is 0.4:100, immersing for 1h at 100rpm, washing for 3 times by using dichloromethane, and drying for 2h in vacuum at the vacuum degree of-0.08 MPa and the temperature of 40 ℃ to obtain a silicon dioxide coating film;
(4) The preparation method comprises the steps of immersing a silicon dioxide coating film in a 1, 4-butane sultone solution with the mass of 50 times that of the silicon dioxide coating film, reacting the 1, 4-butane sultone and tetrahydrofuran in the 1, 4-butane sultone solution at the mass ratio of 0.1:100 at 200rpm and 40 ℃ for 7 hours, washing the film with tetrahydrofuran for 3 times, and vacuum drying the film at the vacuum degree of-0.08 MPa and 40 ℃ for 2 hours to obtain the blue algae scavenger.
Example 2
(1) Mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11.5:6:0.8, stirring for 24 hours at 250rpm, and standing for 12 hours to obtain a shell spinning solution; mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 7:73, stirring for 2 hours at 250rpm and 60 ℃, and standing for 12 hours to obtain a core spinning solution; respectively injecting the shell layer spinning solution and the core layer spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.6mm, the flow rate of the inner tube spinning solution is 1mL/h, the diameter of the outer tube is 1.5mm, the flow rate of the outer tube spinning solution is 1mL/h, the voltage is 20kV and the receiving distance is 20cm to obtain a fiber membrane;
(2) Heating to 600 ℃ at 2 ℃/min, calcining the fiber membrane at high temperature for 1.5 hours, cooling to 450 ℃, spraying a metal ion solution with the mass of 0.15 of the fiber membrane to the fiber membrane, and continuously reacting for 1.5 hours at the mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water in the metal ion solution of 15:7:5:1000 to obtain the modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber film in an N, N-diethyl-3- (trimethoxysilane) propylamine solution with the mass ratio of which is 75 times that of the modified titanium dioxide fiber film, wherein the mass ratio of the N, N-diethyl-3- (trimethoxysilane) propylamine to the dichloromethane is 0.5:100, immersing for 2 hours at 150rpm, washing for 4 times by using the dichloromethane, and drying for 2.5 hours at the vacuum degree of-0.08 MPa and the temperature of 45 ℃ to obtain a silicon dioxide coated film;
(4) The preparation method comprises the steps of immersing a silicon dioxide coating film in a 1, 4-butane sultone solution with the mass ratio of 1, 4-butane sultone to tetrahydrofuran in the 1, 4-butane sultone solution being 0.15:100, reacting for 8 hours at the temperature of 45 ℃ at 250rpm, washing for 4 times with tetrahydrofuran, and vacuum drying for 2.5 hours at the temperature of 45 ℃ at the vacuum degree of-0.08 MPa to obtain the blue algae scavenger.
Example 3
(1) Mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 12:7:0.8, stirring for 24 hours at 300rpm, and standing for 12 hours to obtain a shell spinning solution; mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 8:73, stirring for 2 hours at 300rpm and 65 ℃, and standing for 12 hours to obtain a core spinning solution; respectively injecting the shell layer spinning solution and the core layer spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 1.0mm, the flow rate of the inner tube spinning solution is 1.5mL/h, the diameter of the outer tube is 2mm, the flow rate of the outer tube spinning solution is 1.5mL/h, the voltage is 30kV and the receiving distance is 30cm to obtain a fiber membrane;
(2) Heating to 700 ℃ at 3 ℃/min, calcining the fiber membrane at high temperature for 2 hours, cooling to 500 ℃, spraying a metal ion solution with the mass of 0.2 of the fiber membrane to the fiber membrane, and continuously reacting for 2 hours, wherein the mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water in the metal ion solution is 19:8:9:1000, so as to obtain the modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber film in an N, N-diethyl-3- (trimethoxysilyl) propylamine solution with the mass ratio of which is 100 times that of the modified titanium dioxide fiber film, wherein the mass ratio of the N, N-diethyl-3- (trimethoxysilyl) propylamine to the dichloromethane is 0.6:100, immersing for 3 hours at 200rpm, washing for 5 times by using the dichloromethane, and drying for 3 hours in vacuum at the temperature of 50 ℃ under the vacuum degree of-0.08 MPa to obtain a silicon dioxide coated film;
(4) Immersing the silicon dioxide coating film in a 1, 4-butane sultone solution with the mass of 100 times that of the silicon dioxide coating film, wherein the mass ratio of the 1, 4-butane sultone to the tetrahydrofuran in the 1, 4-butane sultone solution is 0.2:100, reacting for 9 hours at 300rpm and 50 ℃, washing for 5 times by using tetrahydrofuran, and vacuum drying for 3 hours at the vacuum degree of-0.08 MPa and 50 ℃ to obtain the blue algae scavenger.
Comparative example 1
(1) Mixing tetrabutyl titanate and acetone according to a mass ratio of 11.5:6, stirring for 24 hours at 250rpm, and standing for 12 hours to obtain a shell spinning solution; mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 7:73, stirring for 2 hours at 250rpm and 60 ℃, and standing for 12 hours to obtain a core spinning solution; respectively injecting the shell layer spinning solution and the core layer spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.6mm, the flow rate of the inner tube spinning solution is 1mL/h, the diameter of the outer tube is 1.5mm, the flow rate of the outer tube spinning solution is 1mL/h, the voltage is 20kV and the receiving distance is 20cm to obtain a fiber membrane;
(2) Heating to 600 ℃ at 2 ℃/min, calcining the fiber membrane at high temperature for 1.5 hours, cooling to 450 ℃, spraying a metal ion solution with the mass of 0.15 of the fiber membrane to the fiber membrane, and continuously reacting for 1.5 hours at the mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water in the metal ion solution of 15:7:5:1000 to obtain the modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber film in an N, N-diethyl-3- (trimethoxysilane) propylamine solution with the mass ratio of which is 75 times that of the modified titanium dioxide fiber film, wherein the mass ratio of the N, N-diethyl-3- (trimethoxysilane) propylamine to the dichloromethane is 0.5:100, immersing for 2 hours at 150rpm, washing for 4 times by using the dichloromethane, and drying for 2.5 hours at the vacuum degree of-0.08 MPa and the temperature of 45 ℃ to obtain a silicon dioxide coated film;
(4) The preparation method comprises the steps of immersing a silicon dioxide coating film in a 1, 4-butane sultone solution with the mass ratio of 1, 4-butane sultone to tetrahydrofuran in the 1, 4-butane sultone solution being 0.15:100, reacting for 8 hours at the temperature of 45 ℃ at 250rpm, washing for 4 times with tetrahydrofuran, and vacuum drying for 2.5 hours at the temperature of 45 ℃ at the vacuum degree of-0.08 MPa to obtain the blue algae scavenger.
Comparative example 2
(1) Mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11.5:6:0.8, stirring for 24 hours at 250rpm, and standing for 12 hours to obtain spinning solution; carrying out electrostatic spinning on the spinning solution under the conditions that the diameter of a needle tube is 1.5mm, the flow rate is 1mL/h, the voltage is 20kV, and the receiving distance is 20cm, so as to obtain a fiber membrane;
(2) Heating to 600 ℃ at 2 ℃/min, calcining the fiber membrane at high temperature for 1.5 hours, cooling to 450 ℃, spraying a metal ion solution with the mass of 0.15 of the fiber membrane to the fiber membrane, and continuously reacting for 1.5 hours at the mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water in the metal ion solution of 15:7:5:1000 to obtain the modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber film in an N, N-diethyl-3- (trimethoxysilane) propylamine solution with the mass ratio of which is 75 times that of the modified titanium dioxide fiber film, wherein the mass ratio of the N, N-diethyl-3- (trimethoxysilane) propylamine to the dichloromethane is 0.5:100, immersing for 2 hours at 150rpm, washing for 4 times by using the dichloromethane, and drying for 2.5 hours at the vacuum degree of-0.08 MPa and the temperature of 45 ℃ to obtain a silicon dioxide coated film;
(4) The preparation method comprises the steps of immersing a silicon dioxide coating film in a 1, 4-butane sultone solution with the mass ratio of 1, 4-butane sultone to tetrahydrofuran in the 1, 4-butane sultone solution being 0.15:100, reacting for 8 hours at the temperature of 45 ℃ at 250rpm, washing for 4 times with tetrahydrofuran, and vacuum drying for 2.5 hours at the temperature of 45 ℃ at the vacuum degree of-0.08 MPa to obtain the blue algae scavenger.
Comparative example 3
(1) Mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11.5:6:0.8, stirring for 24 hours at 250rpm, and standing for 12 hours to obtain a shell spinning solution; mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 7:73, stirring for 2 hours at 250rpm and 60 ℃, and standing for 12 hours to obtain a core spinning solution; respectively injecting the shell layer spinning solution and the core layer spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.6mm, the flow rate of the inner tube spinning solution is 1mL/h, the diameter of the outer tube is 1.5mm, the flow rate of the outer tube spinning solution is 1mL/h, the voltage is 20kV and the receiving distance is 20cm to obtain a fiber membrane;
(2) Heating to 600 ℃ at 2 ℃/min, calcining the fiber membrane at high temperature for 1.5h, cooling to 450 ℃, and continuing to react for 1.5h to obtain the titanium dioxide fiber membrane;
(3) Immersing a titanium dioxide fiber membrane in an N, N-diethyl-3- (trimethoxysilyl) propylamine solution with the mass ratio of which is 75 times that of the titanium dioxide fiber membrane, wherein the mass ratio of the N, N-diethyl-3- (trimethoxysilyl) propylamine to the dichloromethane is 0.5:100, immersing for 2 hours at 150rpm, washing for 4 times by using the dichloromethane, and drying for 2.5 hours at the vacuum degree of-0.08 MPa and the temperature of 45 ℃ to obtain a silicon dioxide coating membrane;
(4) The preparation method comprises the steps of immersing a silicon dioxide coating film in a 1, 4-butane sultone solution with the mass ratio of 1, 4-butane sultone to tetrahydrofuran in the 1, 4-butane sultone solution being 0.15:100, reacting for 8 hours at the temperature of 45 ℃ at 250rpm, washing for 4 times with tetrahydrofuran, and vacuum drying for 2.5 hours at the temperature of 45 ℃ at the vacuum degree of-0.08 MPa to obtain the blue algae scavenger.
Comparative example 4
(1) Mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11.5:6:0.8, stirring for 24 hours at 250rpm, and standing for 12 hours to obtain a shell spinning solution; mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 7:73, stirring for 2 hours at 250rpm and 60 ℃, and standing for 12 hours to obtain a core spinning solution; respectively injecting the shell layer spinning solution and the core layer spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.6mm, the flow rate of the inner tube spinning solution is 1mL/h, the diameter of the outer tube is 1.5mm, the flow rate of the outer tube spinning solution is 1mL/h, the voltage is 20kV and the receiving distance is 20cm to obtain a fiber membrane;
(2) Heating to 600 ℃ at 2 ℃/min, calcining the fiber membrane at high temperature for 1.5 hours, cooling to 450 ℃, spraying a metal ion solution with the mass of 0.15 of the fiber membrane to the fiber membrane, and continuously reacting for 1.5 hours at the mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water in the metal ion solution of 15:7:5:1000 to obtain the modified titanium dioxide fiber membrane;
(4) Immersing the modified titanium dioxide fiber membrane in a 1, 4-butane sultone solution with the mass of 75 times of that of the modified titanium dioxide fiber membrane, reacting the modified titanium dioxide fiber membrane with tetrahydrofuran at 250rpm and 45 ℃ for 8 hours at the mass ratio of 1, 4-butane sultone to tetrahydrofuran in the 1, 4-butane sultone solution of 0.15:100, washing with tetrahydrofuran for 4 times, and vacuum drying at the vacuum degree of-0.08 MPa and 45 ℃ for 2.5 hours to obtain the blue algae scavenger.
Comparative example 5
(1) Mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11.5:6:0.8, stirring for 24 hours at 250rpm, and standing for 12 hours to obtain a shell spinning solution; mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 7:73, stirring for 2 hours at 250rpm and 60 ℃, and standing for 12 hours to obtain a core spinning solution; respectively injecting the shell layer spinning solution and the core layer spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.6mm, the flow rate of the inner tube spinning solution is 1mL/h, the diameter of the outer tube is 1.5mm, the flow rate of the outer tube spinning solution is 1mL/h, the voltage is 20kV and the receiving distance is 20cm to obtain a fiber membrane;
(2) Heating to 600 ℃ at 2 ℃/min, calcining the fiber membrane at high temperature for 1.5 hours, cooling to 450 ℃, spraying a metal ion solution with the mass of 0.15 of the fiber membrane to the fiber membrane, and continuously reacting for 1.5 hours at the mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water in the metal ion solution of 15:7:5:1000 to obtain the modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber membrane in an N, N-diethyl-3- (trimethoxysilyl) propylamine solution with the mass ratio of which is 75 times that of the modified titanium dioxide fiber membrane, wherein the mass ratio of the N, N-diethyl-3- (trimethoxysilyl) propylamine to the dichloromethane is 0.5:100, immersing for 2 hours at 150rpm, washing for 4 times by using the dichloromethane, and drying for 2.5 hours at the vacuum degree of-0.08 MPa and the temperature of 45 ℃ to obtain the blue algae scavenger.
Effect example
The following table 1 shows the results of performance analysis of blue algae scavengers employing examples 1 to 3 of the present invention and comparative examples 1 to 5.
TABLE 1
As can be seen from the comparison of the data of the algae removal rate in the examples and the comparative examples in the table 1, the algae removal agent prepared by the invention has good algae removal effect, the polyacrylonitrile is used as a fiber membrane formed by fibers with a core layer and tetrabutyl titanate/polyvinylpyrrolidone as a shell layer, after the first high-temperature treatment, the fiber membrane formed by fibers with a mesoporous carbon structure as the core layer and mesoporous titanium dioxide is formed, the specific surface area of the fiber membrane can be increased by the mesoporous structure so as to increase the contact area and the accommodation volume of the fiber membrane on blue algae, the blue algae removal effect of the blue algae scavenger is improved, after the second high-temperature treatment, the core layer of the mesoporous carbon structure is actively carbonized, and meanwhile cobalt ions, boron ions and silver ions are doped into the shell layer titanium dioxide structure, so that the photooxidation capability of the blue algae scavenger is further improved, the first impregnation treatment forms a mesoporous silicon dioxide membrane on the fiber surface, the specific surface area of the fiber membrane is further increased, the quaternary amine structure and the sulfonic acid group are introduced on the fiber membrane surface after the second impregnation treatment, and the blue algae removal effect of the blue algae scavenger can be further improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (6)
1. The blue algae scavenger is characterized in that the blue algae scavenger is prepared by sequentially carrying out a first high-temperature treatment, a second high-temperature treatment, a first dipping treatment and a second dipping treatment on a fiber film;
the first high temperature treatment is as follows: the fiber membrane is treated for a period of time at 500-700 ℃ to obtain a titanium dioxide fiber membrane; the second high temperature treatment is as follows: spraying a metal ion solution on the titanium dioxide fiber membrane, and then treating the titanium dioxide fiber membrane for a period of time at 400-500 ℃ to obtain a modified titanium dioxide fiber membrane;
the first dipping treatment is as follows: immersing the modified titanium dioxide fiber membrane in an N, N-diethyl-3- (trimethoxy silane) propylamine solution for a period of time to obtain a silicon dioxide coating membrane; the second impregnation treatment is as follows: and immersing the silicon dioxide coating film in a 1, 4-butane sultone solution for a period of time to obtain the blue algae scavenger.
2. The blue algae scavenger according to claim 1, wherein the fiber membrane is prepared by coaxial electrostatic spinning of a polyacrylonitrile core spinning solution and a tetrabutyl titanate/polyvinylpyrrolidone shell spinning solution.
3. The preparation method of the blue algae scavenger is characterized by comprising the following preparation steps:
(1) Respectively injecting the shell spinning solution and the core spinning solution into an outer tube and an inner tube of a coaxial spinneret, and carrying out electrostatic spinning under the conditions that the diameter of the inner tube is 0.2-1.0 mm, the flow rate of the inner tube spinning solution is 0.5-1.5 mL/h, the diameter of the outer tube is 1-2 mm, the flow rate of the outer tube spinning solution is 0.5-1.5 mL/h, the voltage is 10-30 kV and the receiving distance is 10-30 cm to obtain a fiber membrane;
(2) Heating to 500-700 ℃ at a speed of 1-3 ℃/min, calcining the fiber membrane at a high temperature for 1-2 hours, cooling to 400-500 ℃, spraying a metal ion solution with a mass of 0.1-0.2 of the fiber membrane to the fiber membrane, and continuously reacting for 1-2 hours at a mass ratio of boric acid, silver nitrate, cobalt nitrate and deionized water of 11:6:1:1000-19:8:9:1000 to obtain a modified titanium dioxide fiber membrane;
(3) Immersing the modified titanium dioxide fiber film in an N, N-diethyl-3- (trimethoxysilyl) propylamine solution with the mass of 50-100 times that of the modified titanium dioxide fiber film, immersing for 1-3 hours at 100-200 rpm, washing for 3-5 times with methylene chloride, and vacuum drying for 2-3 hours at 40-50 ℃ under the vacuum degree of-0.08 MPa to obtain a silicon dioxide coating film;
(4) Immersing the silicon dioxide coating film in a 1, 4-butane sultone solution with the mass of 50-100 times that of the silicon dioxide coating film, wherein the mass ratio of 1, 4-butane sultone to tetrahydrofuran in the 1, 4-butane sultone solution is 0.1:100-0.2:100, reacting for 7-9 hours at the temperature of 40-50 ℃ at 200-300 rpm, washing for 3-5 times by using tetrahydrofuran, and vacuum drying for 2-3 hours at the temperature of 40-50 ℃ at the vacuum degree of-0.08 MPa to obtain the blue algae scavenger.
4. The method for preparing blue algae scavenger according to claim 3, wherein the preparing method of the shell spinning solution in the step (1) comprises the following steps: mixing tetrabutyl titanate, acetone and polyvinylpyrrolidone according to a mass ratio of 11:5:0.8-12:7:0.8, stirring for 24 hours at 200-300 rpm, and standing for 12 hours to obtain a shell spinning solution.
5. The method for preparing blue algae scavenger according to claim 4, wherein the core spinning solution preparation method in step (1) comprises the following steps: mixing polyacrylonitrile and N, N-dimethylformamide according to a mass ratio of 6:73-8:73, stirring for 2 hours at 200-300 rpm and a temperature of 55-65 ℃, and standing for 12 hours to obtain the core spinning solution.
6. The method for preparing blue algae scavenger according to claim 4, wherein the N, N-diethyl-3- (trimethoxysilyl) propylamine solution in the step (3) is prepared by mixing N, N-diethyl-3- (trimethoxysilyl) propylamine and dichloromethane according to a mass ratio of 0.4:100-0.6:100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310564377.9A CN116573708B (en) | 2023-05-18 | 2023-05-18 | Blue algae scavenger and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310564377.9A CN116573708B (en) | 2023-05-18 | 2023-05-18 | Blue algae scavenger and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116573708A CN116573708A (en) | 2023-08-11 |
| CN116573708B true CN116573708B (en) | 2024-01-30 |
Family
ID=87539313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310564377.9A Active CN116573708B (en) | 2023-05-18 | 2023-05-18 | Blue algae scavenger and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116573708B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698730A (en) * | 2012-05-11 | 2012-10-03 | 沈阳化工大学 | Preparation method of hollow boron/cerium co-doped nanometer titanium dioxide fiber material |
| CN104445493A (en) * | 2014-11-03 | 2015-03-25 | 芜湖市祥荣食品有限公司 | Blue alga treatment agent capable of purifying water and preparation method thereof |
| AU2020103787A4 (en) * | 2020-11-30 | 2021-02-11 | Junada (qingdao) Technology Co., Ltd. | SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854868A (en) * | 2016-03-30 | 2016-08-17 | 盐城工学院 | Method for preparing molybdenum doped titanium dioxide film by virtue of sol-gel method |
| US20200048478A1 (en) * | 2018-08-11 | 2020-02-13 | Marcos Gonzalez | Composites having novel anti-fouling components and methods of manufature |
-
2023
- 2023-05-18 CN CN202310564377.9A patent/CN116573708B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698730A (en) * | 2012-05-11 | 2012-10-03 | 沈阳化工大学 | Preparation method of hollow boron/cerium co-doped nanometer titanium dioxide fiber material |
| CN104445493A (en) * | 2014-11-03 | 2015-03-25 | 芜湖市祥荣食品有限公司 | Blue alga treatment agent capable of purifying water and preparation method thereof |
| AU2020103787A4 (en) * | 2020-11-30 | 2021-02-11 | Junada (qingdao) Technology Co., Ltd. | SiO2/PVDF-HFP Composite Fiber Membrane and Its Preparation Method and Application |
Non-Patent Citations (2)
| Title |
|---|
| Photocatalytic degradation effect and mechanism of Karenia mikimotoi by non-noble metal modified TiO2 loading onto copper metal organic framework (SNP-TiO2@Cu-MOF) under visible light;Hu, LJ等;《JOURNAL OF HAZARDOUS MATERIALS》;第442卷;全文 * |
| 基于静电纺丝技术的细胞固载化及其应用;贺盛春;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第4期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116573708A (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103408002B (en) | Microbial reduction of graphene oxide and preparation method for graphene | |
| CN108017793B (en) | Preparation method of slow-release polyurethane reticular carrier and application of slow-release polyurethane reticular carrier in chemical wastewater treatment | |
| CN110217792B (en) | Nitrogen-sulfur-doped hierarchical porous carbon material and preparation method and application thereof | |
| CN112121766A (en) | Ramie fiber-based biochar and preparation method and application thereof | |
| CN116573708B (en) | Blue algae scavenger and preparation method thereof | |
| CN115337448A (en) | Tannin-coupled polyphosphazene-based hydrogel wound dressing with anti-inflammatory, antibacterial and ROS (reactive oxygen species) response performances and preparation method thereof | |
| CN114917943B (en) | Nitrogen-doped magnetic biochar material and preparation method and application thereof | |
| CN112500527A (en) | Preparation method of organic modified fly ash reinforced sodium alginate hydrogel | |
| CN111944799B (en) | Preparation method and application of immobilized particles embedded with Thiobacillus denitrificans | |
| CN103601273B (en) | Nano titanium dioxide modification method of electric adsorption desalinization carbon electrode | |
| CN113046857A (en) | Seawater uranium extraction adsorbent capable of self-renewing active antifouling coating and preparation method thereof | |
| CN112652723A (en) | Polymer blend modified perovskite solar cell and preparation method thereof | |
| CN112044417A (en) | Adsorbing material for treating printing and dyeing wastewater and preparation method thereof | |
| CN112645453A (en) | Composite microbial inoculum for reducing nitrogen content in sewage | |
| CN111499821A (en) | Photosensitive zwitterionic polyurethane, preparation method thereof and preparation method of polyurethane micelle | |
| CN108221371B (en) | Method for preparing antibacterial polyester by using halamine compound and silver ions | |
| CN107805655B (en) | Orange algae artificial turf and application thereof in coupling ammonium nitrogen sewage treatment and carotenoid production | |
| CN110902847B (en) | Production process of carbon fiber ecological grass | |
| CN110773133B (en) | Preparation method of dye wastewater adsorbent and purification method of dye wastewater | |
| CN108773906B (en) | Method for preventing and controlling shallow water system eutrophic lake by using aquatic plants | |
| CN108529753B (en) | Treatment method of slaughter wastewater | |
| CN108529754B (en) | Polyvinyl alcohol-zinc oxide composite microsphere and preparation method and application thereof | |
| CN114349984B (en) | Composite hydrogel for wastewater treatment and preparation method and application thereof | |
| CN113582895B (en) | Quaternary ammonium salt and algicide, and preparation method and application thereof | |
| CN111328836B (en) | Bacillus smearing preparation for preventing and treating grape crown gall |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |