CN107285452B - Method for rapidly degrading antibiotics - Google Patents
Method for rapidly degrading antibiotics Download PDFInfo
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- CN107285452B CN107285452B CN201710450226.5A CN201710450226A CN107285452B CN 107285452 B CN107285452 B CN 107285452B CN 201710450226 A CN201710450226 A CN 201710450226A CN 107285452 B CN107285452 B CN 107285452B
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 31
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 239000013179 MIL-101(Fe) Substances 0.000 claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 44
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000004098 Tetracycline Substances 0.000 claims description 45
- 235000019364 tetracycline Nutrition 0.000 claims description 44
- 229930101283 tetracycline Natural products 0.000 claims description 44
- 150000003522 tetracyclines Chemical class 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000012924 metal-organic framework composite Substances 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 21
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 230000003115 biocidal effect Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000004100 Oxytetracycline Substances 0.000 claims description 6
- 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 6
- 235000019366 oxytetracycline Nutrition 0.000 claims description 6
- 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 6
- OGQYJDHTHFAPRN-UHFFFAOYSA-N 2-fluoro-6-(trifluoromethyl)benzonitrile Chemical compound FC1=CC=CC(C(F)(F)F)=C1C#N OGQYJDHTHFAPRN-UHFFFAOYSA-N 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 229960003185 chlortetracycline hydrochloride Drugs 0.000 claims description 5
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229960004368 oxytetracycline hydrochloride Drugs 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 41
- 230000015556 catabolic process Effects 0.000 abstract description 39
- 230000000694 effects Effects 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229960002180 tetracycline Drugs 0.000 description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 35
- 239000012621 metal-organic framework Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229960000625 oxytetracycline Drugs 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QYAPHLRPFNSDNH-MRFRVZCGSA-N (4s,4as,5as,6s,12ar)-7-chloro-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.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)C3=C(O)C2=C1O QYAPHLRPFNSDNH-MRFRVZCGSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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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
- C02F1/72—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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for rapidly degrading antibiotics; the method uses MIL-101(Fe)/TiO2The composite material is used as a catalyst, persulfate can be catalyzed and activated greatly under a normal-temperature weak light source, and a large amount of sulfate radical free radicals are rapidly generated to degrade antibiotics; the composite material is easy to recover, can still keep a good activation effect after being repeatedly used for many times, and is an environment-friendly material; the method has the advantages of simple equipment, convenient operation, energy consumption saving and short catalysis time, can have extremely high degradation effect on antibiotics under weak natural light in areas with serious haze and insufficient illumination, and has great application prospect in the aspect of degrading antibiotics.
Description
Technical Field
The invention belongs to the technical field of pharmaceutical wastewater treatment, and particularly relates to a pharmaceutical wastewater treatment method based on MIL-101(Fe)/TiO2A method for activating persulfate to rapidly degrade antibiotics by using the composite material under a weak light source.
Background
China is a large country for using antibiotics, water pollution is caused while diseases are treated, the antibiotics in rivers mainly come from pharmaceutical wastewater, aquaculture wastewater, animal wastes and the like, the antibiotics are difficult to degrade under natural light, so that the concentration of the antibiotics is continuously accumulated and increased, and the intake of the antibiotics can cause people and animals to generate drug resistance, generate super bacteria and influence the health of the people and the animals.
The prior method for treating antibiotics in water mainly comprises the following steps: adsorption, catalytic degradation, membrane separation, biological treatment and the like. Based on free radicals of sulphuric acid (SO)4 -Has high efficiency for degradation, has received wide attention at home and abroad in recent years, and is persulfate (S)2O8 2-) Can be activated by ultraviolet light, heat, ultrasound or transition metal to generate SO4 -To prepare the compound. Although the transition metal ions are lower in cost than other activation methods, if the metal ions are directly applied to a water body, the transition metal ions have certain toxicity, secondary pollution is generated, and recycling cannot be achieved, so that people tend to research heterogeneous catalysts to activate persulfate. The metal organic framework composite material is used as a heterogeneous catalyst, avoids secondary pollution to water due to the stability of the metal organic framework composite material in water, can be repeatedly used, and is an environment-friendly novel materialBecoming a research hotspot at home and abroad at present.
The metal organic framework composite material is formed by loading a certain chemical substance on a metal organic framework material, wherein the metal organic framework material is an ordered network structure formed by combining an organic ligand and inorganic metal ions. At present, the metal organic framework material has the highest specific surface area, the lowest crystal density and adjustable pore size and functional structure, is easy to load other substances without changing the structure of the metal organic framework material, and contains a large number of unsaturated metal sites, so that the metal organic framework material can be used for some special applications: adsorption, separation, catalysis, and the like.
The photocatalyst has great dependence on the intensity of a light source, weak light can reduce the efficiency of the photocatalyst in degradation, and for some areas with serious antibiotic pollution, the photocatalyst often has serious haze for a long time, insufficient illumination and slower degradation rate, and if the degradation rate is improved, the light source needs to be applied again to generate energy consumption; although the advanced oxidation method is independent of the light intensity, the half-hour degradation rate is below 90 percent according to the degradation rate reported in the current literature, and the time consumption is not ideal although a large part of photocatalysts have obvious improvement. The invention is based on metal organic framework composite material MIL-101(Fe)/TiO2The persulfate is activated, the degradation efficiency is obviously improved, the antibiotic degradation rate can reach 93 percent in ten minutes, and a wide prospect is provided for antibiotic treatment.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method for rapidly degrading antibiotics by using MIL-101(Fe)/TiO2The composite material activates persulfate under a weak light source to generate a large amount of oxidizing free radicals of sulfuric acid, and the free radicals of sulfuric acid further oxidize and degrade antibiotics in the water body; namely, under normal temperature and a weak light source, adding persulfate as an oxidant into water containing antibiotics, simultaneously adopting a metal organic framework composite material as a heterogeneous catalyst, adding the metal organic framework composite material to efficiently activate the persulfate to quickly generate sulfate radicals, and degrading organic pollutant antibiotics in the water by the sulfate radicals, thereby improving the water quality。
The metal organic framework composite material is MIL-101(Fe)/TiO2。
The metal organic framework composite material MIL-101(Fe)/TiO2The preparation method comprises the following steps:
(1) dissolving raw materials in DMF according to the molar ratio of ferric trichloride hexahydrate, terephthalic acid and titanium dioxide of 1:2: 3-3: 2:1, fully stirring for 1-2 hours, transferring the uniformly stirred solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a forced air drying box, reacting for 2-24 hours at 120-160 ℃, taking out the reaction kettle, and naturally cooling the reaction kettle to room temperature;
(2) after the reaction kettle is cooled, carrying out suction filtration on a product, sequentially washing the product with DMF (dimethyl formamide) and ethanol for three times, and then vacuumizing and drying the product at the temperature of 60-80 ℃ for 12-24 hours; obtaining the metal organic framework composite material MIL-101(Fe)/TiO2。
The persulfate comprises one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
The molar ratio of the persulfate added into the water body to the antibiotics in the water body is 10: 1-40: 1.
The metal organic framework composite material MIL-101(Fe)/TiO2The amount of the additive (B) is 0.1-2 g/L.
The weak light source is 0-500W visible light.
The metal organic framework composite material MIL-101(Fe)/TiO2Can be recycled for many times, and embodies the metal organic framework composite material MIL-101(Fe)/TiO2The maximum catalytic capacity of.
The antibiotic is tetracycline, oxytetracycline or chlortetracycline hydrochloride.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) the invention provides a metal organic framework composite material MIL-101(Fe)/TiO2The preparation method has simple operation, low energy consumption and low price;
(2) the metal organic framework composite material is a porous material, has an unsaturated metal active center, enhances the effect of persulfate on generating sulfuric acid free radicals, and improves the degradation effect of a catalyst on antibiotics;
(3) the heterogeneous catalyst has no selectivity to antibiotics, and is widely applicable;
(4) the catalyst can be repeatedly recycled, and has no secondary pollution;
(5) the invention can be suitable for exerting better degradation effect under a weak light source, and has more obvious rapid degradation effect on the area with insufficient illumination;
(6) the method does not need to consume extra energy including ultrasound, strong light source, heat, electricity and the like, reduces the cost and has wide application prospect.
Drawings
FIG. 1 shows a metal organic framework material MIL-101(Fe)/TiO2Wherein, the A picture and the B picture are different magnifications.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
The invention takes tetracycline as a typical antibiotic, and in order to prove that the invention has no selectivity to target pollutants, oxytetracycline and chlortetracycline hydrochloride are also selected as target antibiotics.
Example 1: the method for rapidly degrading the antibiotics specifically comprises the following steps:
this example illustrates MIL-101(Fe)/TiO prepared at 12h/120 ℃ as the preparation conditions2Catalyst, study of MIL-101(Fe)/TiO2Degradation effects on tetracycline;
(1) metal organic framework composite material MIL-101(Fe)/TiO2The preparation of (1): dissolving ferric trichloride hexahydrate, terephthalic acid and titanium dioxide in a molar ratio of 1:1:1 in 40mLDMF, stirring for 1 hour, transferring the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a forced air drying box, reacting for 12 hours at 120 ℃, taking out the reaction kettle, and naturally cooling the reaction kettle to room temperature. After the reaction kettle is cooled, taking out the product and pumping the product by using a sand core funnelFiltering, repeatedly washing with DMF and ethanol for three times, and vacuum drying at 60 deg.C for 12 hr; obtaining the metal organic framework composite material MIL-101(Fe)/TiO2。
The obtained metal organic framework composite material MIL-101(Fe)/TiO2The scanning electron micrograph of (a) is shown in FIG. 1.
(2) A photochemical reactor is adopted as a simulated visible light source, the light source is 300W natural visible light, potassium persulfate and tetracycline solution with the molar ratio of 20:1 are added into the reactor, 80mg/L tetracycline solution with the solution volume of 50mL in the reactor is kept, and 50mg of MIL-101(Fe)/TiO (titanium oxide) solution is added into the reactor at the same time2Magnetic stirring is carried out in an optical reactor, reaction is carried out under the condition of normal temperature, and fixed-point sampling analysis is carried out;
comparative process 1: the metal organic framework composite material MIL-101(Fe)/TiO is not added into the reactor2The other conditions are the same as the step (2);
comparative process 2: adding no potassium persulfate into the reactor, and performing the same steps (2) under other conditions;
the removal rates for the three processes are shown in table 1.
Table 1: metal organic framework composite material MIL-101(Fe)/TiO2Adsorption degradation effect on tetracycline
As can be seen from Table 1: metal organic framework composite material MIL-101(Fe)/TiO used alone2Or potassium persulfate has no obvious effect on removing tetracycline, but when the metal organic framework composite material MIL-101(Fe)/TiO is added at the same time2And potassium persulfate, the removal rate of tetracycline is obviously and rapidly improved.
Example 2: this example is MIL-101(Fe)/TiO prepared at 12h/120 ℃ preparation conditions2For the catalyst, the influence of different molar ratios of potassium persulfate and tetracycline (n potassium persulfate/n tetracycline =10, 20, 30, 40) on the catalytic activation reaction was investigated;
(1) the preparation method of the metal organic framework composite material is the same as the step (1) in the example 1;
(2) a photochemical reactor is adopted as a simulated visible light source, the light source is 300W natural visible light, potassium persulfate and tetracycline solution with the molar ratio of 10:1 are added into the reactor, 80mg/L tetracycline solution with the solution volume of 50mL in the reactor is kept, and 50mg of MIL-101(Fe)/TiO (titanium oxide) solution is added into the reactor2Magnetic stirring is carried out in an optical reactor, reaction is carried out under the condition of normal temperature, and fixed-point sampling analysis is carried out;
(3) adding a solution of potassium persulfate and tetracycline into the reactor in a molar ratio of 20:1, keeping the volume of the solution in the reactor to be 50mL of 80mg/L tetracycline solution, and carrying out the other conditions in the same step (2);
(4) adding a solution of potassium persulfate and tetracycline in a molar ratio of 30:1 into the reactor, keeping the volume of the solution in the reactor to be 50mL of 80mg/L tetracycline solution, and carrying out the other conditions in the same step (2);
(5) adding a solution of potassium persulfate and tetracycline in a molar ratio of 40:1 into the reactor, maintaining the volume of the solution in the reactor at 50mL of 80mg/L tetracycline solution, and carrying out the same other conditions as in step (2).
The four process removal rates are shown in table 2.
Table 2: comparison of different n-Potassium persulfate/n-Tetracycline input ratios for Tetracycline degradation Effect
As can be seen from Table 2: the reaction degradation rate showed an upward trend as the ratio of n potassium persulfate/n tetracycline was increased, but when the ratio was 20:1, the degradation rate was not changed much, and n potassium persulfate/n tetracycline =20 was the optimum condition from the viewpoint of reaction efficiency and cost.
Example 3: the embodiment is MIL-101(Fe)/TiO prepared under the preparation condition of 12h/120 DEG C2For the catalyst, MIL-101(Fe)/TiO was investigated2Influence of the amount (5 mg, 25mg, 50mg, 75mg, 100 mg) of (A) on the catalytic activation reaction
(1) Metal organic framework compositeMaterial MIL-101(Fe)/TiO2The preparation method of (2) is the same as the step (1) in embodiment 1;
(2) a photochemical reactor is adopted as a simulated visible light source, the light source is 300W natural visible light, potassium persulfate and tetracycline solution with the molar ratio of 20:1 are added into a reactor, 80mg/L tetracycline solution with the solution volume of 50mL in the reactor is kept, 5mg of MIL-101(Fe)/TiO2 is added into the reactor at the same time, magnetic stirring is carried out in the optical reactor, reaction is carried out under the normal temperature condition, and fixed-point sampling analysis is carried out;
(3) add 25mg of MIL-101(Fe)/TiO to the reactor2The other conditions are the same as the step (2);
(4) 50mg of MIL-101(Fe)/TiO was added to the reactor2The other conditions are the same as the step (2);
(5) add 75mg of MIL-101(Fe)/TiO to the reactor2The other conditions are the same as the step (2);
(6) add 100mg of MIL-101(Fe)/TiO to the reactor2The other conditions are the same as the step (2);
the degradation rates of the five processes are shown in table 3 below;
table 3: MIL-101(Fe)/TiO composite material with different metal organic frameworks2Effect of the amount of the additive on the degradation of tetracycline
As can be seen from Table 3: at 20 minutes, MIL-101(Fe)/TiO2The degradation rates of tetracycline at 5mg, 25mg, 50mg, 75mg, and 100mg were 70.3%, 88.2%, 93.4%, 89.8%, and 89.3%, respectively. As can be seen, the degradation rate increases with the addition of the catalyst, and the degradation rate decreases after the addition of the catalyst reaches 50mg, which is in the range of MIL-101(Fe)/TiO2When the dosage is 50mg, the tetracycline degradation effect is best, and the optimal condition is adopted.
Example 4: this example is to investigate the effect of different preparation times (2, 12, 24 h) or temperatures (120, 140, 160 ℃) on the catalytic activation reaction
(1) Metal organic framework composite material MIL-101(Fe)/TiO with different preparation time2The preparation of (1): dissolving ferric trichloride hexahydrate, terephthalic acid and titanium dioxide in a molar ratio of 1:2:3 in 80mLDMF, stirring for 2 hours, transferring the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a forced air drying box, reacting for 2, 12 and 24 hours at 120 ℃, taking out the reaction kettle, and naturally cooling the reaction kettle to room temperature; cooling the reaction kettle, taking out a product, performing suction filtration by using a sand core funnel, repeatedly washing the product with DMF (dimethyl formamide) and ethanol for three times, and performing vacuum drying at 80 ℃ for 24 hours; thus obtaining the metal organic framework composite material MIL-101(Fe)/TiO2；
(2) Metal organic framework composite material MIL-101(Fe)/TiO with different preparation temperatures2The preparation of (1): dissolving ferric trichloride hexahydrate, terephthalic acid and titanium dioxide in a molar ratio of 3:2:1 in 40mLDMF, stirring for 2 hours, transferring the solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a forced air drying box, reacting for 12 hours at 140 ℃ and 160 ℃, taking out the reaction kettle, and naturally cooling the reaction kettle to room temperature; cooling the reaction kettle, taking out a product, performing suction filtration by using a sand core funnel, repeatedly washing the product with DMF (dimethyl formamide) and ethanol for three times, and performing vacuum drying at 80 ℃ for 24 hours; thus obtaining the metal organic framework composite material MIL-101(Fe)/TiO2；
(3) A photochemical reactor is adopted as a simulated visible light source, the light source is 300W natural visible light, potassium persulfate and tetracycline solution with the molar ratio of 20:1 are added into a reactor, the volume of the solution in the reactor is kept to be 50mL of 80mg/L tetracycline solution, and meanwhile, 50mg of MIL-101(Fe)/TiO (TiO) prepared under the condition of 2h/120 ℃ is added into the reactor2Magnetic stirring is carried out in an optical reactor, reaction is carried out under the condition of normal temperature, and fixed-point sampling analysis is carried out;
(4) 50mg of MIL-101(Fe)/TiO prepared at 12h/120 ℃ was added to the reactor2The other conditions are the same as the step (3);
(5) 50mg of M prepared at 24h/120 ℃ are added to the reactorIL-101(Fe)/ TiO2The other conditions are the same as the step (3);
(6) 50mg of MIL-101(Fe)/TiO prepared at 12h/140 ℃ was added to the reactor2The other conditions are the same as the step (3);
(7) 50mg of MIL-101(Fe)/TiO prepared at 12h/160 ℃ was added to the reactor2The other conditions are the same as the step (3);
the degradation rate of the metal framework composite material MIL-101(Fe)/TiO2 obtained by the five processes is shown in Table 4.
Table 4: metal organic framework composite material MIL-101(Fe)/TiO prepared under different time or temperature conditions2Degradation effect on tetracycline
As can be seen from Table 4: after 20 minutes, the optimal preparation temperature is 120 ℃ under the preparation time of 12 hours, and the degradation rate is reduced along with the temperature increase. The optimum reaction time is 12h at a reaction temperature of 120 ℃.
Example 5: this example is a metal organic framework composite MIL-101(Fe)/TiO prepared at 12h/120 deg.C2As a catalyst, the influence of different light source intensities on tetracycline degradation is researched;
(1) metal organic framework composite material MIL-101(Fe)/TiO2The preparation method of (a) is the same as the step (1) in case 1;
(2) adopting a photochemical reactor as a simulated visible light source, not applying the light source, keeping the reactor in a dark state, adding a potassium persulfate and tetracycline solution with a molar ratio of 20:1 into the reactor, keeping the volume of the solution in the reactor to be 50mL of 80mg/L tetracycline solution, and simultaneously adding 50mg of MIL-101(Fe)/TiO (titanium oxide) into the reactor2Magnetic stirring is carried out in an optical reactor, reaction is carried out under the condition of normal temperature, and fixed-point sampling analysis is carried out;
(3) adjusting the light source of the reactor to be 100W visible light, and the other conditions are the same as (2);
(4) adjusting the light source of the reactor to be 300W visible light, and the other conditions are the same as (2);
(5) adjusting the light source of the reactor to be 500W visible light, and the other conditions are the same as (2);
the degradation rates for the four processes are shown in table 5.
Table 5: degradation effect on tetracycline under different light source intensity conditions
As can be seen from Table 5: the maximum degradation rate can be achieved under the weak light sources of 100W and 300W, and the strong light does not contribute to improving the degradation efficiency.
Example 6: the embodiment is MIL-101(Fe)/TiO prepared under the preparation condition of 12h/120 DEG C2For the catalyst, MIL-101(Fe)/TiO was investigated2The effect of cyclic use of (a) on the degradation of tetracycline.
(1) Metal organic framework composite material MIL-101(Fe)/TiO2The preparation method of (a) is the same as the step (1) in case 1;
(2) a photochemical reactor is adopted as a simulated visible light source, the light source is 300W natural visible light, potassium persulfate and tetracycline solution with the molar ratio of 20:1 are added into the reactor, 80mg/L tetracycline solution with the solution volume of 50mL in the reactor is kept, and 50mg of MIL-101(Fe)/TiO (titanium oxide) solution is added into the reactor at the same time2Magnetic stirring is carried out in an optical reactor, reaction is carried out under the condition of normal temperature, and fixed-point sampling analysis is carried out;
(3) after the step (2) is finished, centrifugally separating the catalyst in the reactor at a high speed, drying the catalyst in a drying oven at 100 ℃, and putting the catalyst into a reaction system which is the same as the system in the step (2) for recycling;
the catalyst was used for four cycles, and the results of each cycle on tetracycline degradation are shown in table 6;
table 6: MIL-101(Fe)/TiO2Four cycles comparison of Effect on tetracycline degradation
As can be seen from Table 6: after four cycles, and with loss of catalyst, the metal organic framework composite material MIL-101(Fe)/TiO2The degradation rate for degrading tetracycline is still kept above 90 percent, which shows that MIL-101(Fe)/TiO2Good recyclability.
Example 7: this example is MIL-101(Fe)/TiO prepared at 12h/120 ℃ preparation conditions2For the catalyst, MIL-101(Fe)/TiO was investigated2Influence on degradation of different antibiotics (tetracycline, oxytetracycline, chlortetracycline hydrochloride);
(1) metal organic framework composite material MIL-101(Fe)/TiO2The preparation method of (a) is the same as the step (1) in case 1;
(2) a photochemical reactor is adopted as a simulated visible light source, the light source is 300W natural visible light, potassium persulfate and tetracycline solution with the molar ratio of 20:1 are added into the reactor, 80mg/L tetracycline solution with the solution volume of 50mL in the reactor is kept, and 50mg of MIL-101(Fe)/TiO (titanium oxide) solution is added into the reactor at the same time2Magnetic stirring is carried out in an optical reactor, reaction is carried out under the condition of normal temperature, and fixed-point sampling analysis is carried out;
(3) adding 50mL of 80mg/L oxytetracycline solution into the reactor under the same conditions as in (2);
(4) adding 50mL of 80mg/L aureomycin hydrochloride solution into the reactor under the same other conditions as in the step (2);
the degradation rates for the three processes are shown in table 7;
table 7: MIL-101(Fe)/TiO2Comparison of degradation effects on different antibiotics
As can be seen from Table 7: after 20 minutes, MIL-101(Fe)/TiO2The degradation efficiency of tetracycline, oxytetracycline and chlortetracycline hydrochloride is not very different, which indicates that MIL-101(Fe)/TiO2And the non-selectivity of the antibiotic degradation can degrade various antibiotics.
Claims (3)
1. A method for rapidly degrading antibiotics, which is characterized in that: under normal temperature and a weak light source, adding persulfate as an oxidant into a water body containing antibiotics, simultaneously adopting a metal organic framework composite material as a heterogeneous catalyst, adding the metal organic framework composite material to efficiently activate the persulfate to quickly generate sulfate radicals, and degrading organic pollutant antibiotics in the water body by the sulfate radicals so as to improve the water quality;
the metal organic framework composite material is MIL-101(Fe)/TiO2The metal organic framework composite material is MIL-101(Fe)/TiO2The preparation method comprises the following steps:
(1) dissolving raw materials in DMF according to the molar ratio of ferric trichloride hexahydrate, terephthalic acid and titanium dioxide of 1:2: 3-3: 2:1, fully stirring for 1-2 hours, transferring the uniformly stirred solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a forced air drying box, reacting for 2-24 hours at 120-160 ℃, taking out the reaction kettle, and naturally cooling the reaction kettle to room temperature;
(2) after the reaction kettle is cooled, carrying out suction filtration on a product, sequentially washing the product with DMF (dimethyl formamide) and ethanol for three times, and then carrying out vacuum-pumping drying at the temperature of 60-80 ℃; obtaining the metal organic framework composite material MIL-101(Fe)/TiO2；
The weak light source is 0-500W visible light;
the antibiotic is tetracycline, oxytetracycline or chlortetracycline hydrochloride.
2. The method for rapidly degrading antibiotics according to claim 1, characterized in that: the persulfate comprises one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
3. The method for rapidly degrading antibiotics according to claim 1, characterized in that: the molar ratio of persulfate added into the water body to antibiotics in the water body is 10: 1-40: 1, and the metal organic framework composite material MIL-101(Fe)/TiO2The amount of the additive (B) is 0.1-2 g/L.
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| CN108911009B (en) * | 2018-07-24 | 2020-08-21 | 湖南大学 | Method for removing antibiotics in water body by using nickel-doped metal organic framework material |
| CN109758714B (en) * | 2019-01-23 | 2020-12-18 | 浙江理工大学 | Method for restoring antibiotic-polluted soil |
| CN110483788B (en) * | 2019-07-19 | 2021-11-05 | 中国地质大学（武汉） | MIL-53(Fe) composite material, preparation method thereof and application thereof in tetracycline degradation |
| CN111318260A (en) * | 2020-02-25 | 2020-06-23 | 江苏大学 | TiO22(B) Preparation method and application of/MIL-100 (Fe) composite material |
| CN111530501B (en) * | 2020-05-08 | 2023-07-25 | 五邑大学 | Fe/Zn-MOF-derived magnetic photocatalytic material and preparation method and application thereof |
| ES2884450B2 (en) * | 2020-06-08 | 2022-05-25 | Univ Extremadura | METHOD FOR THE MAGNETIZATION OF INORGANIC SOLIDS |
| CN112250158A (en) * | 2020-09-30 | 2021-01-22 | 华中科技大学 | Method for oxidative degradation of PPCP pollutants by using alcohol-reinforced persulfate system |
| CN113044951B (en) * | 2021-03-19 | 2022-10-21 | 西安交通大学 | Method for degrading antibiotics in water by using plasma in cooperation with sulfite and ferric salt |
| CN114956194A (en) * | 2022-04-22 | 2022-08-30 | 浙江华源颜料股份有限公司 | Iron oxyhydroxide and application thereof in cooperative degradation of antibiotics with persulfate |
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| CN105923738A (en) * | 2016-06-20 | 2016-09-07 | 华南理工大学 | Method for utilizing metal organic skeleton to carry out efficient catalytic activation on persulfate or peroxymonosulfate to process organic wastewater |
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