CN116605973A - Catalyst for treating tetracycline wastewater and preparation method and application thereof - Google Patents
Catalyst for treating tetracycline wastewater and preparation method and application thereof Download PDFInfo
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- CN116605973A CN116605973A CN202310563658.2A CN202310563658A CN116605973A CN 116605973 A CN116605973 A CN 116605973A CN 202310563658 A CN202310563658 A CN 202310563658A CN 116605973 A CN116605973 A CN 116605973A
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- chitosan
- cobalt ferrite
- solution
- coated cobalt
- microsphere
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- 239000004098 Tetracycline Substances 0.000 title claims abstract description 36
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 36
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 36
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 32
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 32
- 239000002351 wastewater Substances 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001661 Chitosan Polymers 0.000 claims abstract description 39
- 239000004005 microsphere Substances 0.000 claims abstract description 34
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 29
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- RDQFKNPNVMUGDT-UHFFFAOYSA-L disodium;acetate;hydroxide Chemical compound [OH-].[Na+].[Na+].CC([O-])=O RDQFKNPNVMUGDT-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000004108 freeze drying Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 239000006228 supernatant Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910003321 CoFe Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 241000282414 Homo sapiens Species 0.000 description 7
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229940040944 tetracyclines Drugs 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 244000144972 livestock Species 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000186361 Actinobacteria <class> Species 0.000 description 1
- 208000031295 Animal disease Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001775 anti-pathogenic effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100001014 gastrointestinal tract lesion Toxicity 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- 230000006950 reactive oxygen species formation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 238000003911 water pollution Methods 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
-
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a catalyst for treating tetracycline waste water, a preparation method and application thereof, wherein a certain proportion of chitosan coated cobalt ferrite microspheres and peroxymonosulfate are added into the tetracycline waste water for degradation treatment under dark conditions; the preparation method of the chitosan coated cobalt ferrite microsphere comprises the following steps: step one, dissolving chitosan in acetic acid to obtain chitosan solution, and adding CoCl 2 ·6H 2 O and FeCl 3 ·6H 2 O is dissolved inObtaining a metal salt solution in deionized water; uniformly mixing the metal salt solution and the chitosan solution, eliminating bubbles, then dropwise adding the mixture into the sodium hydroxide-sodium acetate mixed solution at a certain temperature, continuously reacting for a period of time, and standing and cooling after the reaction is finished; washing the obtained product with deionized water until the pH value of the supernatant is neutral, and then freeze-drying the product to obtain a finished product of the chitosan coated cobalt ferrite microsphere; the microsphere prepared by the invention has stronger magnetism and better magnetic recovery capability.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a catalyst for treating tetracycline wastewater, and a preparation method and application thereof.
Background
In recent years, with the progress of technology and the rapid growth of population, water pollution is continuously increased, and the global water resource condition is continuously deteriorated.
Antibiotics refer to a class of secondary metabolites produced by microorganisms, including bacteria, fungi, actinomycetes, or higher animals and plants, during life, that have antipathogenic or other activities and interfere with the developmental functions of other living cells. At present, antibiotics are widely applied to the fields of medicine, animal disease prevention and treatment, aquaculture, livestock, agriculture and the like, but the absorption capacity of people and livestock to the antibiotics is extremely limited, and meanwhile, due to abuse of the antibiotics, a large amount of antibiotics enter a water body. The application of the tetracycline in various industries of human medicine brings great convenience to human society, but the application and abuse of the tetracycline lead 70% of the tetracycline not to be fully absorbed by animals or human bodies but to be released into the environment, so that the tetracycline is polluted and destroyed. Tetracyclines can disrupt cell ribosome formation and inhibit protein synthesis, thereby producing an inhibitory effect on cell formation. After the tetracycline enters the human body, the tetracycline can form huge poison to cells of some viscera in the human body, and reduce metabolism of the human body. The administration of tetracyclines not only can lead to gastrointestinal lesions, but also can lead to repeated infection of a large number of drug-resistant bacteria, so that human beings can be treated without drugs, and even more and more drug-resistant bacteria can be generated.
Tetracyclines have a stable chemical structure and low biodegradability, and decay periods in the environment are relatively long, which are difficult to effectively remove by conventional water treatment methods. Therefore, it is important to explore an efficient and environmentally friendly method to rapidly remove tetracyclines in an aqueous environment.
Disclosure of Invention
The oxidative degradation capability of the peroxymonosulfate is limited, the chitosan coated cobalt ferrite microsphere can not react with tetracycline, and the self adsorption capability is not strong. Cobalt ferrite can activate the persulfate to produce free radical to degrade tetracycline, but the cobalt ferrite is easy to agglomerate in the process of catalytic reaction, and the defect can be well overcome in a persulfate/chitosan coated cobalt ferrite microsphere system.
In view of the above, the invention provides a tetracycline wastewater treatment method, which utilizes chitosan coated cobalt ferrite microsphere to activate peroxymonosulfate to degrade tetracycline wastewater, specifically, under dark condition, adding a certain proportion of chitosan coated cobalt ferrite microsphere and peroxymonosulfate into the tetracycline wastewater to degrade;
preferably, the mass concentration (g/L) of the catalyst is 1:5 of the mass concentration (mmol/L) of the peroxomonosulfate; most preferably, 0.1g/L chitosan coated cobalt ferrite microsphere and 0.5mmol/L persulfate are added;
the preferred operation is that the degradation treatment is carried out in the constant-temperature oscillation of the gas bath, the preferred temperature is 25 ℃, the preferred rotating speed is 200r/min, and the preferred reaction time is 2h;
the preparation method of the chitosan coated cobalt ferrite microsphere comprises the following steps:
step one, dissolving chitosan in acetic acid to obtain chitosan solution, and adding CoCl 2 ·6H 2 O and FeCl 3 ·6H 2 O is dissolved in deionized water to obtain a metal salt solution;
preferably, chitosan is mixed with acetic acid at a volume concentration of 2% at m: v (g/ml) =1:40, coCl is added 2 ·6H 2 O、FeCl 3 ·6H 2 O is dissolved in deionized water according to the mol ratio of 1:2;
uniformly mixing the metal salt solution and the chitosan solution, eliminating bubbles, then dropwise adding the mixture into the sodium hydroxide-sodium acetate mixed solution at a certain temperature, continuously reacting for a period of time, and standing and cooling to room temperature after the reaction is finished;
preferably, eliminating bubbles by ultrasonic treatment for 20 min;
preferably, the mixture is added into a sodium hydroxide-sodium acetate mixed solution dropwise at the temperature of 85-95 ℃ for 2h of reaction;
preferably, mixing sodium hydroxide, sodium acetate and deionized water according to a mass ratio of 3:1:60;
washing the obtained product with deionized water until the pH value of the supernatant is neutral, and then freeze-drying the product to obtain a catalyst finished product;
preferably, the mixture is freeze-dried at a temperature of-60 ℃ and a vacuum degree of 20Pa for 12 hours.
The material prepared by the process is spherical, has an internal porous structure, can expose more active sites to activate the peroxymonosulfate to generate free radicals, improves the activity of the catalyst, and has better activation capability than the common peroxymonosulfate/chitosan system.
The main active sites on the peroxymonosulfate/chitosan coated cobalt ferrite microsphere material are provided by Fe and Co metal ions, and the catalyst has higher electron transfer capability. H in the reaction process 2 O molecules are physically adsorbed on the microsphere surface and are combined with metal cations Fe 3+ And Co 2+ Combine to form Fe 3+ -OH and Co 2+ -OH, dissolution of the peroxomonosulphate into the system, SO 4 - The sum OH will be instantaneously formed and the tetracycline oxide will be decomposed into CO 2 And H 2 O. At the same time, high valence metal Co 3+ Can form SO with less contribution to tetracycline degradation 5 - ·；Fe 2+ Can also be combined with surface activitySubstance binding, inducing the formation of reactive oxygen species, then through the Fe formed 3+ The reaction between the substance and the peroxymonosulfate produces more Fe 2+ And reactive free radicals, fe 2+ /Fe 3+ And Co 2+ /Co 3+ The cyclic reaction between them is represented by Fenton-like reaction, and the reversible oxidation and reduction maintains the structure and high-performance activation of cobalt ferrite. Can efficiently catalyze the degradation and removal of the tetracycline in the water body by the persulfates.
The reaction of the chitosan coated cobalt ferrite microsphere in the water body comprises the following steps:
Co 2+ -OH+HSO 5 - →Co 3+ -OH+SO 4 - ·+H 2 O
Fe 3+ -OH+HSO 5 - →Fe 2+ -OH+SO 5 - ·+H +
SO 4 - ·+H 2 O→SO 4 2- +H + +·OH
SO 4 - + & OH+TC- & gtintermediate- & gtCO 2 +H 2 O+SO 4 2-
Co 3+ -OH+HSO 5 - →Co 2+ -OH+SO 5 - ·+H +
Fe 2+ -OH+HSO 5 - →Fe 3+ -OH+SO 4 - ·+H 2 O
The invention has the following effects:
(1) The invention has the advantages that the surface metal ions participate in the reaction in the catalytic reaction process, reversible oxidation-reduction reaction exists in the reaction process, and the reaction is catalyzed by the form of intermediate products, although Fe is generated 2+ And Co 3+ But then consume Fe 2+ And Co 3+ So the reaction process maintains CoFe 2 O 4 Structurally stable and high performance peroxymonosulfate activation.
(2) The three-dimensional network structure of the chitosan coated cobalt ferrite microsphere can better effectively solve the problem of easy agglomeration of cobalt ferrite compared with a layered structure and the like, and provides more active sites, so that the chitosan coated cobalt ferrite microsphere has good catalytic performance.
(3) Meanwhile, the hollow microspheres have stronger magnetism and better magnetic recovery capability; after 5 times of cyclic use, the catalyst still has good catalytic performance, the metal ion precipitation rate is low, and secondary pollution to the water body is avoided; is a material extremely suitable for catalyzing the degradation of the tetracycline by the persulfates, and has better prospect in the field of tetracycline degradation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of a microsphere;
FIG. 2 is an X-ray spectroscopy chart of the microspheres;
FIG. 3 is an X-ray diffraction pattern of microspheres;
FIG. 4 is a graph of magnetic strength of microspheres;
FIG. 5 is a graph of pore size distribution of microspheres;
FIG. 6 is a diagram of a Persulfate (PMS), chitosan-coated cobalt ferrite alone (CS/CoFe) 2 O 4 ) Microsphere, PMS/CS/CoFe 2 O 4 System, PMS/CoFe 2 O 4 And the system and the PMS/CS system degrade the tetracycline effect graph.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. 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.
The preparation method of the chitosan coated cobalt ferrite microsphere of the following example and comparative example is as follows:
step one, 1g of chitosan was dissolved in 40mL of 2% acetic acid to obtain a chitosan solution, and 0.01M CoCl was added 2 ·6H 2 O and 0.02M FeCl 3 ·6H 2 O is dissolved in 10mL of deionized water to obtain a metal salt solution;
slowly adding the metal salt solution into the chitosan solution, stirring for 30min by using a magnetic stirrer, and eliminating bubbles by ultrasonic treatment for 20 min; then dripping the obtained solution into a sodium hydroxide/sodium acetate mixed solution at the temperature of 90 ℃, standing and cooling to room temperature after the reaction is finished;
the preparation method of the sodium hydroxide/sodium acetate mixed solution comprises the following steps of dissolving 7.5g of sodium hydroxide and 2.45g of sodium acetate in 150ml of deionized water;
and thirdly, washing the product of the step two by deionized water until the pH value of the decanted supernatant is neutral, and then freeze-drying at the temperature of-60 ℃ and the vacuum degree of 20Pa for 12 hours to obtain a finished product.
Example 1
The whole reaction process is kept dark, 200mL of waste water containing tetracycline is poured into a conical flask, and then 0.1g/L chitosan coated cobalt ferrite microsphere and 0.5mmol/L potassium peroxomonosulphonate (PMS/CS/CoFe) are added into the waste water 2 O 4 The system is characterized in that a conical flask is placed in a gas bath constant temperature oscillating box, the set temperature is 25 ℃, the rotating speed is 200r/min, the reaction time is 2h, the final concentration of TC is measured after the reaction is finished, and the initial concentration of TC is 20mg/L.
Comparative example 1
Unlike example 1, this comparative example only added 0.5mmol/L of potassium peroxymonosulphonate to the wastewater, i.e. "PMS alone" system.
Comparative example 2
Unlike example 1, this comparative example only added 0.2g/L of chitosan-coated cobalt ferrite microspheres, i.e. "CS/CoFe alone", to the wastewater 2 O 4 "System".
Comparative example 3
Unlike example 1The comparative example, however, was carried out by adding 0.2g/L cobalt ferrite and 0.5mmol/L potassium peroxomonosulphonate to the wastewater, i.e. "PMS/CoFe 2 O 4 "System".
Comparative example 4
Unlike example 1, this comparative example added 0.2g/L chitosan and 0.5mmol/L potassium peroxymonosulphonate to the wastewater, i.e. "PMS/CS" system.
According to the graph 2, the carbon (C), oxygen (O), iron (Fe) and cobalt (Co) elements in the material prepared by the invention are uniformly distributed, and the material has high purity without doping other elements; as can be seen from FIG. 3, the diffraction peak of the chitosan coated cobalt ferrite microsphere is compared with that of standard CoFe 2 O 4 Correspondingly, the main crystal phase in the microsphere is CoFe 2 O 4 A phase; according to the graph shown in fig. 4, the characterization shows that the microsphere has better magnetic property, and can be recycled through an external magnetic field; as can be seen from fig. 5, the prepared microsphere has compact structure, rich pore channels, larger specific surface area and pore volume, and is beneficial to providing more active sites in the reaction, thereby improving the catalytic performance;
as can be seen from FIG. 6, the "PMS alone" system had a tetracycline degradation rate of 41.5% and "CS/CoFe alone", with reference to TC removal rate 2 O 4 "the tetracycline degradation rate of the system is 1.2%," PMS/CS/CoFe 2 O 4 "the tetracycline degradation rate of the system is 86.4%," PMS/CoFe 2 O 4 The tetracycline degradation rate of the system is 71.7 percent, and the tetracycline degradation rate of the PMS/CS system is 52.6 percent;
in five groups of systems, "PMS/CS/CoFe 2 O 4 The system has the strongest tetracycline degradation capability, namely the chitosan coated cobalt ferrite microsphere and the peroxymonosulfate system.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for treating tetracycline waste water is characterized in that a catalyst and persulphate with a certain proportion are added into the tetracycline waste water for degradation treatment under a dark condition, and the catalyst is chitosan coated cobalt ferrite microspheres.
2. The method for treating tetracycline wastewater as defined in claim 1, wherein 0.1g of catalyst and 0.5mmol of peroxymonosulfate are added per liter of wastewater.
3. A method for preparing the chitosan coated cobalt ferrite microsphere according to claim 1, comprising the following steps:
step one, dissolving chitosan in acetic acid to obtain chitosan solution, and adding CoCl 2 ·6H 2 O and FeCl 3 ·6H 2 O is dissolved in deionized water to obtain a metal salt solution;
uniformly mixing the metal salt solution and the chitosan solution, eliminating bubbles, then dropwise adding the mixture into the sodium hydroxide-sodium acetate mixed solution at a certain temperature, continuously reacting for a period of time, and standing and cooling to room temperature after the reaction is finished;
and thirdly, washing the obtained product by deionized water until the pH value of the supernatant is neutral, and then freeze-drying the product to obtain the finished product of the chitosan coated cobalt ferrite microsphere.
4. A method according to claim 3, wherein in step one, chitosan is mixed with acetic acid having a volume concentration of 2% in m:v (g/ml) =1:40, coCl 2 ·6H 2 O and FeCl 3 ·6H 2 The O molar ratio was 1:2.
5. A process according to claim 3, wherein in step two the reaction is carried out at a temperature of 85-95 ℃ for 2 hours.
6. A production method according to claim 3, wherein sodium hydroxide, sodium acetate and deionized water are mixed in a mass ratio of 3:1:60 to produce a sodium hydroxide-sodium acetate mixed solution.
7. A process according to claim 3, wherein in step three, the mixture is freeze-dried at a temperature of-60 ℃ and a vacuum of 20Pa for 12 hours.
8. A chitosan-coated cobalt ferrite microsphere prepared by the method of any one of claims 3-7.
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| WO2020109304A1 (en) * | 2018-11-28 | 2020-06-04 | Consejo Superior De Investigaciones Científicas (Csic) | Preparation method for preparing a catalyst based on iron nanoparticles, cobalt nanoparticles or alloys thereof, the catalyst thus prepared and use of the catalyst for the selective hydrogenation of carbon dioxide to isobutane |
| CN112264096A (en) * | 2020-11-23 | 2021-01-26 | 陕西科技大学 | Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof |
| CN113145177A (en) * | 2021-01-20 | 2021-07-23 | 陕西科技大学 | Hydrotalcite/chitosan composite spherical catalyst, preparation method and application |
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| CN113559909A (en) * | 2021-07-27 | 2021-10-29 | 陕西科技大学 | Magnetic LDO/CN composite catalyst and preparation method and application thereof |
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| WO2020109304A1 (en) * | 2018-11-28 | 2020-06-04 | Consejo Superior De Investigaciones Científicas (Csic) | Preparation method for preparing a catalyst based on iron nanoparticles, cobalt nanoparticles or alloys thereof, the catalyst thus prepared and use of the catalyst for the selective hydrogenation of carbon dioxide to isobutane |
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