CN113731373A - Chitosan non-woven fabric adsorbent with fluorescence indication function and application thereof - Google Patents
Chitosan non-woven fabric adsorbent with fluorescence indication function and application thereof Download PDFInfo
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- CN113731373A CN113731373A CN202111090225.7A CN202111090225A CN113731373A CN 113731373 A CN113731373 A CN 113731373A CN 202111090225 A CN202111090225 A CN 202111090225A CN 113731373 A CN113731373 A CN 113731373A
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- woven fabric
- tetracycline
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- zinc
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 99
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 97
- 239000003463 adsorbent Substances 0.000 title claims abstract description 55
- 239000004098 Tetracycline Substances 0.000 claims abstract description 57
- 229960002180 tetracycline Drugs 0.000 claims abstract description 57
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 56
- 229930101283 tetracycline Natural products 0.000 claims abstract description 56
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 56
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000003795 desorption Methods 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 229940072172 tetracycline antibiotic Drugs 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- SGKRLCUYIXIAHR-AKNGSSGZSA-N (4s,4ar,5s,5ar,6r,12ar)-4-(dimethylamino)-1,5,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4a,5,5a,6-tetrahydro-4h-tetracene-2-carboxamide Chemical compound C1=CC=C2[C@H](C)[C@@H]([C@H](O)[C@@H]3[C@](C(O)=C(C(N)=O)C(=O)[C@H]3N(C)C)(O)C3=O)C3=C(O)C2=C1O SGKRLCUYIXIAHR-AKNGSSGZSA-N 0.000 claims description 2
- 239000004099 Chlortetracycline Substances 0.000 claims description 2
- 239000004100 Oxytetracycline Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 claims description 2
- 229960004475 chlortetracycline Drugs 0.000 claims description 2
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 claims description 2
- 235000019365 chlortetracycline Nutrition 0.000 claims description 2
- 229960003722 doxycycline Drugs 0.000 claims description 2
- 229960000625 oxytetracycline Drugs 0.000 claims description 2
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 claims description 2
- 235000019366 oxytetracycline Nutrition 0.000 claims description 2
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000011701 zinc Substances 0.000 abstract description 26
- 229910052725 zinc Inorganic materials 0.000 abstract description 26
- 230000008021 deposition Effects 0.000 abstract description 25
- 238000001179 sorption measurement Methods 0.000 abstract description 18
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- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 206010070834 Sensitisation Diseases 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000008313 sensitization Effects 0.000 abstract description 4
- 230000000007 visual effect Effects 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 5
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- 239000006228 supernatant Substances 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
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- 238000005286 illumination Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229920005615 natural polymer Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000009374 poultry farming Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Images
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
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- Water Treatment By Sorption (AREA)
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Abstract
The invention discloses a chitosan non-woven fabric adsorbent with a fluorescence indication function and application thereof in tetracycline wastewater treatment. The preparation method of the chitosan non-woven fabric adsorbent comprises the following steps: firstly, soaking the chitosan non-woven fabric in a zinc salt solution, stirring at room temperature, taking out the chitosan non-woven fabric, and then washing and drying to obtain the zinc-deposited chitosan non-woven fabric adsorbent. The method is simple to implement, environment-friendly, low in cost, good in effect of removing tetracycline pollutants in water, capable of using alkali liquor for desorption, easy to regenerate and recycle, and green and efficient. In addition, as the tetracycline is colorless and transparent, the adsorption saturation state is difficult to distinguish by naked eyes, the fluorescence sensitization condition under ultraviolet light after the zinc deposition chitosan non-woven fabric adsorbs the tetracycline can be observed, the enrichment degree of trace tetracycline on the surface of the non-woven fabric adsorption material can be effectively judged, and a good visual indication effect is achieved.
Description
Technical Field
The invention relates to a preparation method of a chitosan non-woven adsorbent with a fluorescence indication function, which is suitable for adsorbing trace tetracycline pollutants in water and has an adsorption quantity indication function.
Background
Nowadays, with the rapid development of medical science and technology, more and more medicinal products enter the environmental water body through domestic sewage, culture wastewater and other ways. Antibiotic drugs also present a class of "persistent" states in environmental waters due to frequent use and constant discharge of humans, livestock and poultry farming and aquaculture. Currently, reports of antibiotic contamination in surface water, ground water, and even drinking water are very common worldwide. The persistent presence of antibiotics and their metabolites in aqueous environments will selectively kill some environmental microorganisms and induce the production of some drug-resistant flora, causing unpredictable damage to the ecological environment and human health. Although antibiotic pollutants do not belong to persistent organic pollutants, the general chemical and biological methods are difficult to work due to the very low concentration of the pollutants in water (usually between ng.L < -1 > and mug.L < -1 >), and the decomposition and degradation processes are limited by the impossibility of kinetics, thereby bringing new challenges to the conventional water pollution control technology.
The chitosan macromolecule is basic polysaccharide which exists most widely in nature, is widely derived from crustaceans such as shrimps, crabs and the like, and is a low-value agricultural product with rich resources. The structure of the chitosan material contains abundant active amino and hydroxyl, and can effectively form a polymer-metal complex by complexing with metal ions, and simultaneously, the capability of metal elements participating in electron transfer and transportation and the outstanding natural polymer characteristics of the chitosan material are fused. The tetracycline antibiotics are two major antibiotic medicines which are produced and used in the world at present, and the molecules of the tetracycline antibiotics contain a famous beta-diketone group with a ligand structure, and can be coordinated with all metal ions almost because of very strong coordination capacity, so that the tetracycline antibiotics are very beneficial to the construction of a chitosan-metal ion-tetracycline ternary complex system. By utilizing stronger specific coordination among ternary complex systems, the selective adsorption of low-concentration tetracycline antibiotics is expected to be realized. Meanwhile, as the nonwoven fabric weaving technology has become mature, the nonwoven fabric manufactured by using chitosan as a raw material has been commercially produced. The characteristics similar to the woven fabric enable the chitosan non-woven fabric to be easily separated and conveniently replaced in flowing water, and the method is very suitable for the water treatment process.
On the other hand, metal ions such as zinc can be coordinately bound with tetracycline antibiotics, and also have strong fluorescence sensitization effect on the tetracycline antibiotics. The chitosan has certain fluorescence property, the fluorescence property of the chitosan-metal complex can be obviously changed after the chitosan-metal complex adsorbs tetracycline, and the fluorescence intensity is in direct proportion to the adsorption quantity of the tetracycline, so that the adsorption saturation state of the chitosan non-woven fabric can be indicated.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a chitosan adsorbent with an indicating function and is applied to the adsorption of low-concentration tetracycline in water.
In order to solve the technical problems, the invention provides a chitosan non-woven fabric adsorbent with a fluorescence indication function, which is characterized in that the preparation method comprises the following steps: firstly, soaking the chitosan non-woven fabric in a zinc salt solution, stirring at room temperature, taking out the chitosan non-woven fabric, and then washing and drying to obtain the zinc-deposited chitosan non-woven fabric adsorbent.
Preferably, the zinc salt solution contains zinc chloride, zinc sulfate and zinc nitrate; the pH range of the zinc salt solution is 4-6.
More preferably, the concentrations of the zinc chloride, the zinc sulfate and the zinc nitrate are all 1-10 mmol/L.
Preferably, the stirring time at room temperature is 6-12 h; the drying temperature is 40-80 ℃.
The invention also provides application of the chitosan non-woven fabric adsorbent with the fluorescence indication function in tetracycline wastewater treatment.
Preferably, the chitosan non-woven fabric adsorbent is used for treating tetracycline wastewater, then the chitosan non-woven fabric is treated by a desorption agent, and the chitosan non-woven fabric is reused after tetracycline desorption.
More preferably, the desorbent is HCl solution.
Further, the concentration of the HCl solution is 0.01 mol/L.
Preferably, the concentration of the tetracycline antibiotics in the tetracycline waste water is 1 × 10-7～5×10-6mol/L。
Preferably, the tetracycline antibiotics contained in the tetracycline waste water comprise at least one of tetracycline, chlortetracycline, oxytetracycline or doxycycline.
When the non-woven fabric is soaked in the zinc solution, the chitosan non-woven fabric and zinc ions are coordinated in a certain proportion, so that the proper zinc ion concentration needs to be selected. When the concentration of the zinc ions is too low, the zinc ions combined with the chitosan non-woven fabric are less, and sufficient adsorption active sites cannot be provided; too high zinc ion concentration easily causes unnecessary zinc ions which can not be combined with the chitosan non-woven fabric to cause waste, and too high zinc salt solution concentration can cause the pH of the solution to be lower, so that the chitosan non-woven fabric is dissolved. The chitosan non-woven fabric subjected to zinc impregnation treatment simultaneously combines the structural advantages of organic polymers and the capability of metal ions for electron transfer and transportation, can receive lone-pair electrons and is in coordination combination with organic matters providing electrons, and therefore trace tetracycline in water is effectively removed. Meanwhile, by utilizing the fluorescence sensitization effect of zinc ions on tetracycline, the chitosan non-woven fabric can emit fluorescence with different characteristics under ultraviolet light according to different tetracycline binding capacities, and the visual indication of the adsorption state can be realized.
The invention provides a preparation method of a zinc deposition chitosan non-woven fabric adsorbing material with an adsorption quantity indicating function and an application of removing trace tetracycline pollutants in water by combining excellent adsorption performance of a chitosan metal complex adsorbent, excellent separation performance of a non-woven fabric material and a fluorescence sensitization effect of metal ions on tetracycline.
The chitosan non-woven fabric adsorbent prepared by the method is simple to operate when tetracycline pollutants in water are removed, the non-woven fabric is directly thrown into the wastewater, the high-efficiency adsorption of the tetracycline can be completed by stirring at room temperature, and the adsorbed zinc deposition chitosan non-woven fabric adsorbent can be desorbed by treating with a weak acid solution, so that the regeneration of the zinc deposition chitosan non-woven fabric adsorbent is realized. The adsorption condition of tetracycline on the chitosan non-woven fabric can be observed through the fluorescence color and the fluorescence intensity by using an ultraviolet lamp with the wavelength of 365 nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the chitosan non-woven fabric adsorbing material is simple in preparation method and low in cost;
(2) the chitosan non-woven fabric adsorbing material is easy to separate and replace from a water body, and is more suitable for large-scale practical application than a powder chitosan adsorbing material;
(3) the chitosan non-woven fabric adsorbent prepared by the invention is suitable for adsorbing treatment of tetracycline pollutants with lower concentration, and is convenient to operate;
(4) the chitosan non-woven fabric prepared by the invention can observe the enrichment degree of colorless tetracycline on the surface of the non-woven fabric adsorption material through the change of the fluorescence characteristics, and plays a good visual indication role.
Drawings
FIG. 1 is a photograph of chitosan nonwoven fabric adsorbed with tetracycline in room under natural light and 365nm ultraviolet radiation.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
0.5g of chitosan non-woven fabric is soaked in 5mmol/L zinc chloride solution, the mixture is continuously stirred for 12 hours at room temperature, and the zinc deposition chitosan non-woven fabric adsorbent is obtained after washing and drying.
As can be seen from FIG. 1, under indoor natural light, the chitosan non-woven fabric has no obvious color change after adsorbing tetracycline, and the adsorption condition cannot be observed; under 365 ultraviolet irradiation, the fluorescence color of the chitosan non-woven fabric is changed from bluish purple to yellow green along with the increase of the tetracycline adsorption amount, and the fluorescence intensity is gradually enhanced.
Example 2
Soaking 0.5g of chitosan non-woven fabric in 10mmol/L zinc chloride solution, continuously stirring for 12h at room temperature, washing and drying to obtain the chitosan non-woven fabric adsorbent.
Example 3
Soaking 0.5g of chitosan non-woven fabric in 1mmol/L zinc chloride solution, continuously stirring for 12h at room temperature, washing and drying to obtain the chitosan non-woven fabric adsorbent.
Example 4
0.5g of chitosan non-woven fabric is soaked in 5mmol/L zinc nitrate solution, the mixture is continuously stirred for 12 hours at room temperature, and the zinc deposition chitosan non-woven fabric adsorbent is obtained after washing and drying.
Example 5
Soaking 0.5g of chitosan non-woven fabric in 5mmol/L zinc sulfate solution, continuously stirring for 12h at room temperature, washing and drying to obtain the zinc deposition chitosan non-woven fabric adsorbent.
Comparative example 1
0.5g of chitosan non-woven fabric is taken as an adsorbent material.
Comparative example 2
0.5g of chitosan non-woven fabric is soaked in 0.1mmol/L zinc chloride solution, the mixture is continuously stirred for 12 hours at room temperature, and the calcium deposition chitosan non-woven fabric adsorbent is obtained after washing and drying.
Comparative example 3
Soaking 0.5g of chitosan non-woven fabric in 5mmol/L ferric chloride solution, continuously stirring for 12h at room temperature, washing and drying to obtain the iron deposition chitosan non-woven fabric adsorbent.
Comparative example 4
Soaking 0.5g of chitosan non-woven fabric in 5mmol/L magnesium chloride solution, continuously stirring for 12h at room temperature, washing and drying to obtain the magnesium deposition chitosan non-woven fabric adsorbent.
Comparative example 5
Soaking 0.5g of chitosan non-woven fabric in 5mmol/L aluminum chloride solution, continuously stirring for 6 hours at room temperature, and washing and drying to obtain the aluminum deposition chitosan non-woven fabric adsorbent.
Test one: 0.5g of the modified chitosan nonwoven fabric materials prepared in examples 1-5 and comparative examples 1-5 were added to 200mL of 10-6Stirring the solution of tetracycline at 100rpm at room temperature to react, collecting the supernatant, detecting the residual concentration of tetracycline by using a high performance liquid chromatograph, and reading the fluorescence intensity at 520nm of emission wavelength by using a solid fluorescence spectrometer at 365nm of excitation wavelength. The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the modification of zinc ion and the concentration of zinc ion are important for the efficient removal of tetracycline and the fluorescent indication of the amount of adsorbed tetracycline. When the concentration of the zinc ions is too low, the zinc ions combined with the chitosan non-woven fabric are less, and sufficient adsorption active sites cannot be provided; too high zinc ion concentration easily causes unnecessary zinc ions which can not be combined with the chitosan non-woven fabric to cause waste, and too high zinc salt solution concentration can cause the pH of the solution to be lower, so that the chitosan non-woven fabric is dissolved.
And (2) test II: 0.5g of the adsorbent material prepared in example 1 and comparative example 1 was added to 200mL of the adsorbent material having a concentration of 5X 10-7mol/L、1×10-6mol/L、2×10-6mol/L、5×10-6Stirring the tetracycline solution at room temperature for 90 minutes in mol/L, taking supernatant, detecting the residual concentration of the tetracycline by using high performance liquid chromatography, and reading the fluorescence intensity at the emission wavelength of 520nm by using a solid fluorescence spectrometer at the excitation wavelength of 365 nm. The results are shown in Table 2.
TABLE 2
As shown in Table 2, the zinc deposited chitosan nonwoven material prepared in example 1 has a wide application range of tetracycline concentration, namely 5X 10-7～10-6The removal efficiency of more than 70 percent can be achieved between mol/L, and the adsorption quantity is in direct proportion to the fluorescence intensity of the chitosan non-woven fabric under 365nm ultraviolet illumination.
And (3) test III: 0.5g of the adsorbent material prepared in example 1 and comparative example 1 was added to 200mL of 10-6To a solution of tetracycline in mol/L, the mixture was stirred at room temperature for 90 minutes. The adsorbent was reused 5 times as above, and the supernatant was taken to determine the residual concentration of tetracycline. The tetracycline removal results are shown in table 3.
TABLE 3
As can be seen from Table 3, the chitosan nonwoven material still maintains good tetracycline removal effect after being reused for 5 times; in contrast, the chitosan nonwoven material containing no zinc has a low tetracycline removal efficiency.
Example 6
The chitosan non-woven fabric adsorbent was prepared in the same manner as in example 1. 0.5g zinc deposition chitosan non-woven fabric adsorbent is added into 200mL of 10-concentration adsorbent-6Adsorbing the tetracycline solution for 90 minutes at room temperature, washing, and drying the non-woven fabric at 40 ℃ to obtain the tetracycline-adsorbed adsorbent. The used zinc deposition chitosan non-woven fabric adsorbent is put into 50mL of 0.01mol/L HCl aqueous solution, stirred and desorbed tetracycline adsorbed by the zinc deposition chitosan non-woven fabric.
Comparative example 6
Chitosan non-woven fabric adsorbent and preparation method of example 1The formula is the same. 0.5g zinc deposition chitosan non-woven fabric adsorbent is added into 200mL of 10-concentration adsorbent-6Adsorbing the tetracycline solution for 90 minutes at room temperature, washing, and drying the non-woven fabric at 40 ℃ to obtain the tetracycline-adsorbed adsorbent. The used zinc deposition chitosan non-woven fabric adsorbent is put into 50mL of 0.01mol/L NaHCO3Stirring in water solution, desorbing tetracycline adsorbed by chitosan nonwoven fabric with zinc deposition, and then using 1 × 10-4And (4) activating mmol/L HCl and then regenerating and recycling.
Comparative example 7
The zinc deposition chitosan non-woven fabric adsorbent was prepared in the same manner as in example 1. 0.5g zinc deposition chitosan non-woven fabric adsorbent is added into 200mL of 10-concentration adsorbent-6Adsorbing the tetracycline solution for 90 minutes at room temperature, washing, and drying the non-woven fabric at 40 ℃ to obtain the tetracycline-adsorbed adsorbent. The used zinc deposition chitosan non-woven fabric adsorbent is put into 50mL of 0.01mol/L Na2CO3Stirring in water solution, desorbing tetracycline adsorbed by chitosan nonwoven fabric with zinc deposition, and then using 1 × 10-4And (4) activating mmol/L HCl and then regenerating and recycling.
Comparative example 8
The zinc deposition chitosan non-woven fabric adsorbent was prepared in the same manner as in example 1. 0.5g zinc deposition chitosan non-woven fabric adsorbent is added into 200mL of 10-concentration adsorbent-6Adsorbing the tetracycline solution for 90 minutes at room temperature, washing, and drying the non-woven fabric at 40 ℃ to obtain the tetracycline-adsorbed adsorbent. The used zinc deposition chitosan non-woven fabric adsorbent is put into 50mL of 0.01mol/L NaOH aqueous solution, stirred, desorbed tetracycline adsorbed by the zinc deposition chitosan non-woven fabric, and then used by 1 × 10-4And (4) activating mmol/L HCl and then regenerating and recycling.
And (5) testing: and respectively taking the desorption liquid selected in the example 6 and the comparative examples 6-7 to desorb the corresponding adsorbent adsorbed with the tetracycline. The tetracycline desorption results are shown in table 4.
TABLE 4
As can be seen from table 4, the adsorbed chitosan adsorbent can achieve a good desorption effect through desorption of the HCl aqueous solution, and is favorable for recycling.
Claims (10)
1. A chitosan non-woven fabric adsorbent with a fluorescence indication function is characterized in that the preparation method comprises the following steps: firstly, soaking the chitosan non-woven fabric in a zinc salt solution, stirring at room temperature, taking out the chitosan non-woven fabric, and then washing and drying to obtain the zinc-deposited chitosan non-woven fabric adsorbent.
2. The chitosan nonwoven fabric adsorbent with fluorescence indication function of claim 1, wherein the zinc salt solution contains zinc chloride, zinc sulfate and zinc nitrate; the pH range of the zinc salt solution is 4-6.
3. The chitosan non-woven fabric adsorbent with fluorescence indication function of claim 2, wherein the concentrations of zinc chloride, zinc sulfate and zinc nitrate are all 1-10 mmol/L.
4. The chitosan non-woven fabric adsorbent with the fluorescence indication function of claim 1, wherein the stirring time at room temperature is 6-12 h; the drying temperature is 40-80 ℃.
5. The use of the chitosan non-woven fabric adsorbent with fluorescence indication function of any one of claims 1 to 4 in tetracycline wastewater treatment.
6. The use of claim 5, wherein the chitosan non-woven fabric adsorbent is used for treating tetracycline wastewater, and then the chitosan non-woven fabric is treated by a desorption agent and reused after tetracycline desorption.
7. The use of claim 6, wherein the desorbent is HCl solution.
8. The use according to claim 7, wherein the HCl solution has a concentration of 0.01 mol/L.
9. The use of claim 5, wherein the concentration of tetracycline antibiotics in the tetracycline waste water is 1 x 10-7～5×10-6mol/L。
10. The use of claim 5 or 9, wherein the tetracycline antibiotic contained in the tetracycline waste water comprises at least one of tetracycline, chlortetracycline, oxytetracycline, or doxycycline.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114397294A (en) * | 2022-01-13 | 2022-04-26 | 东南大学 | Preparation method of tetracycline sensor based on chitosan nanofiber membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820585A (en) * | 2016-04-08 | 2016-08-03 | 东北林业大学 | Preparation of mesoporous molecular imprinting fluorescent probe and detection of tetracycline antibiotics by mesoporous molecular imprinting fluorescent probe |
| CN106237998A (en) * | 2016-07-28 | 2016-12-21 | 东华大学 | A kind of al deposition chitosan non-woven fabrics adsorbent and preparation thereof and application |
| CN112169755A (en) * | 2020-09-24 | 2021-01-05 | 武汉理工大学 | Preparation method of hydrothermally synthesized zinc chloride activated magnetic sludge biochar applied to tetracycline removal in water |
| CN113150772A (en) * | 2021-04-12 | 2021-07-23 | 广东石油化工学院 | Zn/H2aip fluorescent probe, preparation and application thereof in detection of tetracycline antibiotics |
| CN113201325A (en) * | 2021-04-15 | 2021-08-03 | 江苏大学 | Preparation method of ratio type fluorescent probe and application of ratio type fluorescent probe in tetracycline antibiotic detection |
-
2021
- 2021-09-17 CN CN202111090225.7A patent/CN113731373A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820585A (en) * | 2016-04-08 | 2016-08-03 | 东北林业大学 | Preparation of mesoporous molecular imprinting fluorescent probe and detection of tetracycline antibiotics by mesoporous molecular imprinting fluorescent probe |
| CN106237998A (en) * | 2016-07-28 | 2016-12-21 | 东华大学 | A kind of al deposition chitosan non-woven fabrics adsorbent and preparation thereof and application |
| CN112169755A (en) * | 2020-09-24 | 2021-01-05 | 武汉理工大学 | Preparation method of hydrothermally synthesized zinc chloride activated magnetic sludge biochar applied to tetracycline removal in water |
| CN113150772A (en) * | 2021-04-12 | 2021-07-23 | 广东石油化工学院 | Zn/H2aip fluorescent probe, preparation and application thereof in detection of tetracycline antibiotics |
| CN113201325A (en) * | 2021-04-15 | 2021-08-03 | 江苏大学 | Preparation method of ratio type fluorescent probe and application of ratio type fluorescent probe in tetracycline antibiotic detection |
Non-Patent Citations (1)
| Title |
|---|
| CHENSI SHEN ET AL.: "Selective adsorption and fluorescence sensing of tetracycline by Znmediated chitosan non-woven fabric", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114397294A (en) * | 2022-01-13 | 2022-04-26 | 东南大学 | Preparation method of tetracycline sensor based on chitosan nanofiber membrane |
| CN114397294B (en) * | 2022-01-13 | 2023-12-29 | 东南大学 | Preparation method of tetracycline sensor based on chitosan nanofiber membrane |
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