CN111995789A - Hydrophilic resin for catalytic degradation of antibiotics and preparation method and application thereof - Google Patents
Hydrophilic resin for catalytic degradation of antibiotics and preparation method and application thereof Download PDFInfo
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- CN111995789A CN111995789A CN202010219706.2A CN202010219706A CN111995789A CN 111995789 A CN111995789 A CN 111995789A CN 202010219706 A CN202010219706 A CN 202010219706A CN 111995789 A CN111995789 A CN 111995789A
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 51
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 51
- 229920005989 resin Polymers 0.000 title claims abstract description 48
- 239000011347 resin Substances 0.000 title claims abstract description 48
- 230000015556 catabolic process Effects 0.000 title claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims description 18
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 38
- 230000003115 biocidal effect Effects 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000000593 degrading effect Effects 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000005187 foaming Methods 0.000 claims abstract description 14
- ZPAICLPTNKAJHB-UHFFFAOYSA-M sodium;4-ethenylbenzoate Chemical compound [Na+].[O-]C(=O)C1=CC=C(C=C)C=C1 ZPAICLPTNKAJHB-UHFFFAOYSA-M 0.000 claims abstract description 14
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920006327 polystyrene foam Polymers 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 40
- 239000012071 phase Substances 0.000 claims description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000013049 sediment Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- AGFVQXSUESKCTB-UHFFFAOYSA-N n-[dimethyl(prop-2-enyl)silyl]-n-ethylethanamine Chemical compound CCN(CC)[Si](C)(C)CC=C AGFVQXSUESKCTB-UHFFFAOYSA-N 0.000 claims description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000004098 Tetracycline Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000003285 pharmacodynamic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001775 anti-pathogenic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000023611 glucuronidation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000006241 metabolic reaction Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- -1 β -aminoethyl- γ -aminopropyl Chemical group 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- 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
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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Abstract
The invention relates to a hydrophilic resin for catalyzing and degrading antibiotics, a preparation method and application thereof, wherein the preparation method of the hydrophilic resin comprises the following steps: (1) preparing nano modified titanium dioxide; (2) mixing nano modified titanium dioxide, a styrene monomer, a sodium p-styrenesulfonate monomer, a sodium p-styrenecarboxylate monomer and an initiator, reacting for 3-5 h at 90-92 ℃, and curing at 95-96 ℃ for 20-40min to obtain polystyrene resin; (3) and (3) foaming the polystyrene resin to obtain the polystyrene foam. The preparation method is simple, high in treatment efficiency and short in treatment time, remarkably shortens the degradation time of the antibiotics, reduces the treatment cost of the antibiotic wastewater, and reduces the pollution to the environment; can effectively catalyze and degrade residual antibiotics in the wastewater, is green and environment-friendly, is easy to separate and recycle, can be recycled, and has good application prospect in the treatment of antibiotic wastewater.
Description
Technical Field
The invention relates to the technical field of hydrophilic resin materials, in particular to a hydrophilic resin for catalyzing and degrading antibiotics, and a preparation method and application thereof.
Background
Antibiotics are a class of secondary metabolic organisms produced by bacteria, molds, or other microorganisms during life that have anti-pathogenic or other physiological activities. Antibiotics are used in large quantities for long-term treatment of diseases in humans and animals, and play an important role in securing human health and promoting the development of animal husbandry. Currently, over ten thousand tons of antibiotic drugs are used worldwide for the prevention and treatment of animal diseases each year. The antibiotics can not be completely absorbed by livestock after being ingested, but rather, a considerable part of the antibiotics are discharged into the environment along with the excrement and urine in the form of original drugs or metabolites. According to statistics, 25-75% of the antibiotics used by livestock and poultry are discharged out of the body in the form of parent drugs, and even can reach 90% and 95%. The antibiotics enter various water bodies through ways of fertilizing, medical wastewater discharge and the like, and further pollute soil and sediments.
The usage amount of antibiotics in China is very large, and data shows that the antibiotics in the prescription of the medicine in China account for 70%, and compared with 30% of antibiotics in the western countries, the abuse condition of the antibiotics in China is serious. After the antibiotic is absorbed by organism, a small part of the antibiotic is subjected to metabolic reactions such as hydroxylation, cracking, glucuronidation and the like to generate inactive products, and more than 90 percent of the antibiotic is discharged to the outside of the body in the original shape through excrement and urine and enters into water environment. Water environment pollution and treatment become the focus of social attention, and finding a strategy for treating antibiotic-containing wastewater efficiently, economically and pertinently is a key and difficult point of research. Therefore, new technology and new process for treating antibiotic wastewater with strong pertinence are actively researched and developed by combining the characteristics of water quality and water quantity change of antibiotic wastewater in antibiotic wastewater treatment in future, and the method has great significance for accelerating the construction of resource-saving and environment-friendly society.
The prior method for treating antibiotic production wastewater mainly comprises the following steps: physical chemical method, biological method, wherein the biochemical pretreatment method includes hydrolytic acidification method, anaerobic method, but wherein the high concentration antibiotic wastewater is directly contacted with the microorganism in the pretreatment technology, wherein the growth of resistance genes can be promoted, and the drug-resistant bacteria, the drug-resistant genes and the undegraded antibiotic can bring important safety hazard when the treated wastewater and the residual sludge enter the environment.
In order to solve the potential safety hazard possibly brought, remove antibiotic residues and resistance genes possibly caused by biochemical treatment, and the like, the pharmacodynamic functional group of the antibiotic is efficiently and selectively destroyed under the action of high temperature and strong alkali, so that the pharmacodynamic functional group of the antibiotic is greatly reduced. In addition, due to the large molecular size of the antibiotic compounds, the adsorption removal effect of materials such as activated carbon commonly used in water treatment is not ideal, so that the development of a new technical method for removing the pollutants is necessary. Researches show that the special properties of the nano material, such as huge specific surface area, adjustable pore size structure and modifiable surface property, aim to develop a hydrophilic resin with strong adsorption and degradation capacity on antibiotics, not only can overcome the weak adsorption characteristic of the traditional material, but also has strong operability, and has important significance in the catalytic degradation of antibiotics in water by utilizing the hydrophilic resin containing the nano catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the hydrophilic resin for catalyzing and degrading the antibiotics, which has high antibiotic removal efficiency and low antibiotic residue and obviously reduces the biological toxicity of the antibiotic production wastewater; the invention also aims to provide a preparation method and application of the hydrophilic resin for catalyzing and degrading the antibiotics.
In order to realize the technical purpose, the provided technical scheme is as follows:
a preparation method of a hydrophilic resin for catalyzing and degrading antibiotics comprises the following steps:
(1) mixing ethyl acetate, titanium tetrachloride and N-propanol, stirring for 5-15min, adding N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, allyl (diethylamino) dimethylsilane and span 80, and stirring for 1-2 hours to obtain an oil phase solution; dissolving sodium dodecyl benzene sulfonate in water, and stirring for 5-15min to obtain a water phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 12-24 hours; after the reaction is finished, centrifugally separating the reaction liquid, collecting bottom sediment, washing the bottom sediment with water, and drying for 24-36 hours to obtain nano modified titanium dioxide;
(2) mixing nano modified titanium dioxide, a styrene monomer, a sodium p-styrenesulfonate monomer, a sodium p-styrenecarboxylate monomer and an initiator, reacting for 3-5 h at 90-92 ℃, and curing at 95-96 ℃ for 20-40min to obtain polystyrene resin;
(3) and (3) foaming the polystyrene resin to obtain the polystyrene foam.
Preferably, the preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 2.5-3.5 g of ethyl acetate, 5-8 g of titanium tetrachloride and 10-16 g of N-propanol, stirring for 5-15min at 300-600 revolutions per minute, adding 0.1-0.2 g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, 0.1-0.2 g of allyl (diethylamino) dimethylsilane and 800.2-0.5 g of span, and continuously stirring for 1-2 hours at 300-600 revolutions per minute to obtain an oil phase solution; dissolving 0.2-0.5 g of sodium dodecyl benzene sulfonate in 350-450 g of water, and stirring for 5-15min at 300-600 rpm to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 12-24 hours at 300-600 revolutions per minute; after the reaction is finished, centrifugally separating the reaction liquid, collecting bottom sediment, washing the bottom sediment with water, and drying at 40-50 ℃ for 24-36 hours to obtain nano modified titanium dioxide;
(2) mixing 1-2 g of nano modified titanium dioxide, 2-4 g of styrene monomer, 4-6 g of sodium p-styrenesulfonate monomer, 5-7 g of sodium p-styrenecarboxylate monomer and 0.2-0.4 g of initiator, reacting at 90-92 ℃ for 3-5 h, and curing at 95-96 ℃ for 20-40min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a pre-foaming machine with vapor pressure of 0.1-0.5 MPa and preheating to 70-90 ℃ for foaming, and curing for 5-10 hours to obtain the polystyrene resin.
Preferably, the initiator is a peroxide initiator and/or an azo initiator.
Preferably, the peroxide initiator is at least one of benzoyl peroxide, ammonium persulfate, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
Preferably, the azo initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the mass ratio of the polystyrene resin to the n-pentane in the step (3) is 1: 0.01-0.1.
Preferably, the mass ratio of the polystyrene resin to the n-pentane in the step (3) is 1 to (0.04-0.06).
The invention also provides a hydrophilic resin for catalyzing and degrading antibiotics, and the hydrophilic resin is prepared by adopting the method.
The invention also provides application of the hydrophilic resin for catalyzing and degrading the antibiotics in treatment of wastewater containing the antibiotics.
Specifically, the application method of the hydrophilic resin for catalytic degradation of the antibiotics in treatment of the antibiotic-containing wastewater comprises the steps of adding the hydrophilic resin for catalytic degradation of the antibiotics into the antibiotic-containing wastewater according to the mass ratio of 1: 50-500, uniformly mixing, illuminating for 2-20 hours under the condition of visible light with the wavelength lambda of more than 420nm, carrying out photocatalytic degradation reaction, and filtering and recycling the hydrophilic resin for catalytic degradation of the antibiotics after the photocatalytic degradation reaction is completed.
The invention has the beneficial effects that:
(1) in the preparation process of the hydrophilic resin, on one hand, the compatibility of the titanium dioxide and the polystyrene resin is improved by modifying the titanium dioxide, on the other hand, a great deal of research is carried out on the preparation method of the titanium dioxide, and a specific surfactant and a silane coupling agent are also added.
(2) The inventor of the invention discovers through a large number of experiments that the use amount ratio of the coupling agent is adjusted in the scheme, the pore size of the surface of the obtained nano modified titanium dioxide catalyst is different, the specific surface area of the catalyst is greatly influenced, the nano modified titanium dioxide catalyst has a better pore structure, the adsorption and enrichment capacity on antibiotics is improved, the dispersion of the catalyst can be promoted, the agglomeration of nano particles is reduced, and the prepared hydrophilic resin can be subjected to catalytic degradation on the surface of the hydrophilic resin by the antibiotics under the irradiation of visible light.
(3) The preparation method is simple, high in treatment efficiency and short in treatment time, remarkably shortens the degradation time of the antibiotics, reduces the treatment cost of the antibiotic wastewater, and reduces the pollution to the environment; can effectively catalyze and degrade residual antibiotics in the wastewater, is green and environment-friendly, is easy to separate and recycle, can be recycled, and has good application prospect in the treatment of antibiotic wastewater.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1
The preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 3.0g of ethyl acetate, 7.0g of titanium tetrachloride and 15.0g of N-propanol, stirring for 10min at 400 r/min, adding 0.15g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, 0.15g of allyl (diethylamino) dimethylsilane and 800.35 g of span, and continuously stirring for 1.5 hours at 400 r/min to obtain an oil phase solution; dissolving 0.3g of sodium dodecyl benzene sulfonate in 400g of water, and stirring for 10min at 400 revolutions per minute to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 20 hours at the speed of 400 revolutions per minute; after the reaction is finished, centrifugally separating the reaction solution, collecting bottom sediment, washing the bottom sediment with water, and drying at 45 ℃ for 30 hours to obtain nano modified titanium dioxide;
(2) mixing 1.5g of nano modified titanium dioxide, 3.0g of styrene monomer, 5.0g of sodium p-styrene sulfonate monomer, 6.0g of sodium p-styrene carboxylate monomer and 0.3g of benzoyl peroxide, reacting at 91 ℃ for 4 hours, and curing at 96 ℃ for 30min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a prefoamer with vapor pressure of 0.3MPa and preheated to 80 ℃ for foaming, and curing for 8 hours to obtain hydrophilic resin for catalyzing and degrading antibiotics; the mass ratio of the polystyrene resin to the n-pentane is 1: 0.05.
Comparative example 1
The only difference compared to example 1 is that N- (β -aminoethyl- γ -aminopropyl) methyldimethoxysilane and allyl (diethylamino) dimethylsilane are not added in step (1).
The preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 3.0g of ethyl acetate, 7.0g of titanium tetrachloride and 15.0g of n-propanol, stirring at 400 revolutions per minute for 10min, adding 800.35 g of span, and continuously stirring at 400 revolutions per minute for 1.5 hours to obtain an oil phase solution; dissolving 0.3g of sodium dodecyl benzene sulfonate in 400g of water, and stirring for 10min at 400 revolutions per minute to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 20 hours at the speed of 400 revolutions per minute; after the reaction is finished, centrifugally separating the reaction solution, collecting bottom sediment, washing the bottom sediment with water, and drying at 45 ℃ for 30 hours to obtain nano modified titanium dioxide;
(2) mixing 1.5g of nano modified titanium dioxide, 3.0g of styrene monomer, 5.0g of sodium p-styrene sulfonate monomer, 6.0g of sodium p-styrene carboxylate monomer and 0.3g of benzoyl peroxide, reacting at 91 ℃ for 4 hours, and curing at 96 ℃ for 30min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a prefoamer with vapor pressure of 0.3MPa and preheated to 80 ℃ for foaming, and curing for 8 hours to obtain hydrophilic resin for catalyzing and degrading antibiotics; the mass ratio of the polystyrene resin to the n-pentane is 1: 0.05.
Comparative example 2
Compared with example 1, the only difference is that "0.15 g of N- (. beta. -aminoethyl-. gamma. -aminopropyl) methyldimethoxysilane and 0.15g of allyl (diethylamino) dimethylsilane" are replaced by "0.30 g of N- (. beta. -aminoethyl-. gamma. -aminopropyl) methyldimethoxysilane" in step (1).
The preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 3.0g of ethyl acetate, 7.0g of titanium tetrachloride and 15.0g of N-propanol, stirring at 400 revolutions per minute for 10min, adding 0.30g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane and 800.35 g of span, and continuing to stir at 400 revolutions per minute for 1.5 hours to obtain an oil phase solution; dissolving 0.3g of sodium dodecyl benzene sulfonate in 400g of water, and stirring for 10min at 400 revolutions per minute to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 20 hours at the speed of 400 revolutions per minute; after the reaction is finished, centrifugally separating the reaction solution, collecting bottom sediment, washing the bottom sediment with water, and drying at 45 ℃ for 30 hours to obtain nano modified titanium dioxide;
(2) mixing 1.5g of nano modified titanium dioxide, 3.0g of styrene monomer, 5.0g of sodium p-styrene sulfonate monomer, 6.0g of sodium p-styrene carboxylate monomer and 0.3g of benzoyl peroxide, reacting at 91 ℃ for 4 hours, and curing at 96 ℃ for 30min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a prefoamer with vapor pressure of 0.3MPa and preheated to 80 ℃ for foaming, and curing for 8 hours to obtain hydrophilic resin for catalyzing and degrading antibiotics; the mass ratio of the polystyrene resin to the n-pentane is 1: 0.05.
Comparative example 3
Compared with example 1, the only difference is that "0.15 g of N- (. beta. -aminoethyl-. gamma. -aminopropyl) methyldimethoxysilane and 0.15g of allyl (diethylamino) dimethylsilane" are replaced with "0.30 g of allyl (diethylamino) dimethylsilane" in step (1).
The preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 3.0g of ethyl acetate, 7.0g of titanium tetrachloride and 15.0g of n-propanol, stirring for 10min at 400 r/min, adding 0.30g of allyl (diethylamino) dimethyl silane and 800.35 g of span, and continuously stirring for 1.5 h at 400 r/min to obtain an oil phase solution; dissolving 0.3g of sodium dodecyl benzene sulfonate in 400g of water, and stirring for 10min at 400 revolutions per minute to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 20 hours at the speed of 400 revolutions per minute; after the reaction is finished, centrifugally separating the reaction solution, collecting bottom sediment, washing the bottom sediment with water, and drying at 45 ℃ for 30 hours to obtain nano modified titanium dioxide;
(2) mixing 1.5g of nano modified titanium dioxide, 3.0g of styrene monomer, 5.0g of sodium p-styrene sulfonate monomer, 6.0g of sodium p-styrene carboxylate monomer and 0.3g of benzoyl peroxide, reacting at 91 ℃ for 4 hours, and curing at 96 ℃ for 30min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a prefoamer with vapor pressure of 0.3MPa and preheated to 80 ℃ for foaming, and curing for 8 hours to obtain hydrophilic resin for catalyzing and degrading antibiotics; the mass ratio of the polystyrene resin to the n-pentane is 1: 0.05.
Comparative example 4
The only difference compared to example 1 is that span 80 is not added in step (1).
The preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 3.0g of ethyl acetate, 7.0g of titanium tetrachloride and 15.0g of N-propanol, stirring for 10min at 400 revolutions per minute, adding 0.15g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane and 0.15g of allyl (diethylamino) dimethylsilane, and continuously stirring for 1.5 hours at 400 revolutions per minute to obtain an oil phase solution; dissolving 0.3g of sodium dodecyl benzene sulfonate in 400g of water, and stirring for 10min at 400 revolutions per minute to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 20 hours at the speed of 400 revolutions per minute; after the reaction is finished, centrifugally separating the reaction solution, collecting bottom sediment, washing the bottom sediment with water, and drying at 45 ℃ for 30 hours to obtain nano modified titanium dioxide;
(2) mixing 1.5g of nano modified titanium dioxide, 3.0g of styrene monomer, 5.0g of sodium p-styrene sulfonate monomer, 6.0g of sodium p-styrene carboxylate monomer and 0.3g of benzoyl peroxide, reacting at 91 ℃ for 4 hours, and curing at 96 ℃ for 30min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a prefoamer with vapor pressure of 0.3MPa and preheated to 80 ℃ for foaming, and curing for 8 hours to obtain hydrophilic resin for catalyzing and degrading antibiotics; the mass ratio of the polystyrene resin to the n-pentane is 1: 0.05.
Comparative example 5
Compared with example 1, the difference is only that in the step (2), "5.0 g of sodium p-styrenesulfonate monomer, 6.0g of sodium p-styrenecarboxylate monomer" is replaced with "11.0 g of sodium p-styrenesulfonate monomer".
The preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 3.0g of ethyl acetate, 7.0g of titanium tetrachloride and 15.0g of N-propanol, stirring for 10min at 400 r/min, adding 0.15g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, 0.15g of allyl (diethylamino) dimethylsilane and 800.35 g of span, and continuously stirring for 1.5 hours at 400 r/min to obtain an oil phase solution; dissolving 0.3g of sodium dodecyl benzene sulfonate in 400g of water, and stirring for 10min at 400 revolutions per minute to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 20 hours at the speed of 400 revolutions per minute; after the reaction is finished, centrifugally separating the reaction solution, collecting bottom sediment, washing the bottom sediment with water, and drying at 45 ℃ for 30 hours to obtain nano modified titanium dioxide;
(2) mixing 1.5g of nano modified titanium dioxide, 3.0g of styrene monomer, 11.0g of sodium styrene sulfonate monomer and 0.3g of benzoyl peroxide, reacting at 91 ℃ for 4h, and curing at 96 ℃ for 30min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a prefoamer with vapor pressure of 0.3MPa and preheated to 80 ℃ for foaming, and curing for 8 hours to obtain hydrophilic resin for catalyzing and degrading antibiotics; the mass ratio of the polystyrene resin to the n-pentane is 1: 0.05.
Comparative example 6
Compared with example 1, the difference is only that "5.0 g of sodium p-styrenesulfonate monomer and 6.0g of sodium p-styrenecarboxylate monomer" in step (2) are replaced with "11.0 g of sodium p-styrenecarboxylate monomer".
The preparation method of the hydrophilic resin for catalyzing and degrading the antibiotic comprises the following steps:
(1) mixing 3.0g of ethyl acetate, 7.0g of titanium tetrachloride and 15.0g of N-propanol, stirring for 10min at 400 r/min, adding 0.15g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, 0.15g of allyl (diethylamino) dimethylsilane and 800.35 g of span, and continuously stirring for 1.5 hours at 400 r/min to obtain an oil phase solution; dissolving 0.3g of sodium dodecyl benzene sulfonate in 400g of water, and stirring for 10min at 400 revolutions per minute to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 20 hours at the speed of 400 revolutions per minute; after the reaction is finished, centrifugally separating the reaction solution, collecting bottom sediment, washing the bottom sediment with water, and drying at 45 ℃ for 30 hours to obtain nano modified titanium dioxide;
(2) mixing 1.5g of nano modified titanium dioxide, 3.0g of styrene monomer, 11.0g of sodium p-styrene carboxylate monomer and 0.3g of benzoyl peroxide, reacting at 91 ℃ for 4h, and curing at 96 ℃ for 30min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a prefoamer with vapor pressure of 0.3MPa and preheated to 80 ℃ for foaming, and curing for 8 hours to obtain hydrophilic resin for catalyzing and degrading antibiotics; the mass ratio of the polystyrene resin to the n-pentane is 1: 0.05.
Test example
And (2) adding 1000mg of the hydrophilic resin for catalyzing and degrading the antibiotics prepared in the example 1 and the comparative examples 1-6 into 100mL of tetracycline solution with the concentration of 20mg/L, carrying out ultrasonic homogenization, reacting for 60min under a dark condition (magnetic stirring), after adsorption and desorption balance is achieved, illuminating for 150min under a visible light condition with the wavelength lambda being more than 420nm, and carrying out a photocatalytic degradation reaction to finish the photocatalytic degradation of the tetracycline in the water body. After the photocatalytic degradation reaction is finished, collecting the residual sample, drying, and carrying out photocatalytic degradation on the tetracycline water body under the same experimental conditions for 4 times in total. Sampling 3mL every 30min, measuring the characteristic peak value of tetracycline in the solution by using an ultraviolet-visible spectrophotometer, converting the characteristic peak value into concentration, and calculating the degradation rate of different cycles. Specific results are shown in table 1.
Table 1: test result table
| A degradation rate% | |
| Example 1 | 98.2 |
| Comparative example 1 | 50.5 |
| Comparative example 2 | 50.3 |
| Comparative example 3 | 41.1 |
| Comparative example 4 | 55.9 |
| Comparative example 5 | 68.4 |
| Comparative example 6 | 50.7 |
The ranges of values for the parameter conditions involved in the embodiments of the invention are achievable, and not to be limited by the space, further recitation of endpoints and intermediate values.
The above examples are only intended to illustrate the technical solutions of the present invention to be effective and feasible, but not to limit the same; the technical solutions described in the foregoing embodiments are modified or part of the technical solutions are generally changed and replaced by those skilled in the art, which are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a hydrophilic resin for catalyzing and degrading antibiotics is characterized by comprising the following steps:
(1) mixing ethyl acetate, titanium tetrachloride and N-propanol, stirring for 5-15min, adding N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, allyl (diethylamino) dimethylsilane and span 80, and stirring for 1-2 hours to obtain an oil phase solution; dissolving sodium dodecyl benzene sulfonate in water, and stirring for 5-15min to obtain a water phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 12-24 hours; after the reaction is finished, centrifugally separating the reaction liquid, collecting bottom sediment, washing the bottom sediment with water, and drying for 24-36 hours to obtain nano modified titanium dioxide;
(2) mixing nano modified titanium dioxide, a styrene monomer, a sodium p-styrenesulfonate monomer, a sodium p-styrenecarboxylate monomer and an initiator, reacting for 3-5 h at 90-92 ℃, and curing at 95-96 ℃ for 20-40min to obtain polystyrene resin;
(3) and (3) foaming the polystyrene resin to obtain the polystyrene foam.
2. The method for preparing a hydrophilic resin for catalytic degradation of antibiotics according to claim 1, wherein:
(1) mixing 2.5-3.5 g of ethyl acetate, 5-8 g of titanium tetrachloride and 10-16 g of N-propanol, stirring for 5-15min at 300-600 revolutions per minute, adding 0.1-0.2 g of N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, 0.1-0.2 g of allyl (diethylamino) dimethylsilane and 800.2-0.5 g of span, and continuously stirring for 1-2 hours at 300-600 revolutions per minute to obtain an oil phase solution; dissolving 0.2-0.5 g of sodium dodecyl benzene sulfonate in 350-450 g of water, and stirring for 5-15min at 300-600 rpm to obtain an aqueous phase solution; pouring the obtained oil phase solution into the water phase solution, and stirring and reacting for 12-24 hours at 300-600 revolutions per minute; after the reaction is finished, centrifugally separating the reaction liquid, collecting bottom sediment, washing the bottom sediment with water, and drying at 40-50 ℃ for 24-36 hours to obtain nano modified titanium dioxide;
(2) mixing 1-2 g of nano modified titanium dioxide, 2-4 g of styrene monomer, 4-6 g of sodium p-styrenesulfonate monomer, 5-7 g of sodium p-styrenecarboxylate monomer and 0.2-0.4 g of initiator, reacting at 90-92 ℃ for 3-5 h, and curing at 95-96 ℃ for 20-40min to obtain polystyrene resin;
(3) mixing polystyrene resin and n-pentane, adding the mixture into a pre-foaming machine with vapor pressure of 0.1-0.5 MPa and preheating to 70-90 ℃ for foaming, and curing for 5-10 hours to obtain the polystyrene resin.
3. The process for the preparation of hydrophilic resins for the catalytic degradation of antibiotics according to claim 1 or 2, characterized in that: the initiator is a peroxide initiator and/or an azo initiator.
4. The method for preparing a hydrophilic resin for catalytic degradation of antibiotics according to claim 3, wherein: the peroxide initiator is at least one of benzoyl peroxide, ammonium persulfate, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
5. The method for preparing a hydrophilic resin for catalytic degradation of antibiotics according to claim 3, wherein: the azo initiator is at least one of azodiisobutyronitrile and azodiisoheptonitrile.
6. The process for the preparation of hydrophilic resins for the catalytic degradation of antibiotics according to claim 1 or 2, characterized in that: in the step (3), the mass ratio of the polystyrene resin to the n-pentane is 1: 0.01-0.1.
7. The method for preparing the hydrophilic resin for catalytic degradation of antibiotics according to claim 6, wherein: in the step (3), the mass ratio of the polystyrene resin to the n-pentane is 1: 0.04-0.06.
8. A hydrophilic resin for catalytic degradation of antibiotics, characterized by: prepared by the method of any one of claims 1 to 7.
9. Use of a hydrophilic resin for catalytic degradation of antibiotics according to claim 1 or 2 in the treatment of antibiotic-containing wastewater.
10. The application of the hydrophilic resin for catalytic degradation of antibiotics in treatment of antibiotic-containing wastewater according to claim 9 is that the hydrophilic resin for catalytic degradation of antibiotics is added into the antibiotic-containing wastewater according to the mass ratio of 1: 50-500, the mixture is uniformly mixed, the photocatalytic degradation reaction is performed under the condition of visible light with the wavelength lambda of more than 420nm for 2-20 h, and after the photocatalytic degradation reaction is completed, the hydrophilic resin for catalytic degradation of antibiotics is filtered and recovered.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827392A (en) * | 2012-05-18 | 2012-12-19 | 北京化工大学 | Preparation method of water expanded polystyrene |
| CN106268968A (en) * | 2016-09-28 | 2017-01-04 | 中南林业科技大学 | A kind of preparation method and application of chitosan loaded composite titania material |
| CN106311195A (en) * | 2015-07-06 | 2017-01-11 | 新加坡国立大学 | Catalyst for photocatalytic degradation of antibiotic as well as preparation method and application thereof |
| CN107792911A (en) * | 2017-11-03 | 2018-03-13 | 宁夏大学 | A kind of method for going in water removal to remain tetracycline using absorption method |
| CN108786889A (en) * | 2018-06-21 | 2018-11-13 | 上海电力学院 | A kind of preparation method of the composite material of efficient absorption-photocatalytic degradation antibiotic |
| US20190002309A1 (en) * | 2017-06-30 | 2019-01-03 | The Regents Of The University Of California | Surfactant-assisted synthesis of surface-functionalized nanoparticle-polymer electrospun composites |
| CN110862120A (en) * | 2019-11-27 | 2020-03-06 | 湖南大学 | Method for treating antibiotic wastewater by utilizing visible light response semiconductor-MOFs hybrid photoelectrocatalysis material electrode |
-
2020
- 2020-03-25 CN CN202010219706.2A patent/CN111995789B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827392A (en) * | 2012-05-18 | 2012-12-19 | 北京化工大学 | Preparation method of water expanded polystyrene |
| CN106311195A (en) * | 2015-07-06 | 2017-01-11 | 新加坡国立大学 | Catalyst for photocatalytic degradation of antibiotic as well as preparation method and application thereof |
| CN106268968A (en) * | 2016-09-28 | 2017-01-04 | 中南林业科技大学 | A kind of preparation method and application of chitosan loaded composite titania material |
| US20190002309A1 (en) * | 2017-06-30 | 2019-01-03 | The Regents Of The University Of California | Surfactant-assisted synthesis of surface-functionalized nanoparticle-polymer electrospun composites |
| CN107792911A (en) * | 2017-11-03 | 2018-03-13 | 宁夏大学 | A kind of method for going in water removal to remain tetracycline using absorption method |
| CN108786889A (en) * | 2018-06-21 | 2018-11-13 | 上海电力学院 | A kind of preparation method of the composite material of efficient absorption-photocatalytic degradation antibiotic |
| CN110862120A (en) * | 2019-11-27 | 2020-03-06 | 湖南大学 | Method for treating antibiotic wastewater by utilizing visible light response semiconductor-MOFs hybrid photoelectrocatalysis material electrode |
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