CN108483556A - A method of degradation antibiotic - Google Patents
A method of degradation antibiotic Download PDFInfo
- Publication number
- CN108483556A CN108483556A CN201810177551.3A CN201810177551A CN108483556A CN 108483556 A CN108483556 A CN 108483556A CN 201810177551 A CN201810177551 A CN 201810177551A CN 108483556 A CN108483556 A CN 108483556A
- Authority
- CN
- China
- Prior art keywords
- tio
- mil
- antibiotic
- magnetic
- degradation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 35
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 33
- 230000015556 catabolic process Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000005389 magnetism Effects 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 230000000593 degrading effect Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 84
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 54
- 239000004098 Tetracycline Substances 0.000 claims description 27
- 229960002180 tetracycline Drugs 0.000 claims description 27
- 235000019364 tetracycline Nutrition 0.000 claims description 27
- 229930101283 tetracycline Natural products 0.000 claims description 27
- 150000003522 tetracyclines Chemical class 0.000 claims description 27
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000013177 MIL-101 Substances 0.000 claims description 5
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 claims description 5
- 229960003405 ciprofloxacin Drugs 0.000 claims description 5
- 229940063650 terramycin Drugs 0.000 claims description 5
- 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 claims description 4
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000002955 isolation Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 39
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- -1 sulphuric acid free radical Chemical class 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- HZYWFQBABNUAAP-UHFFFAOYSA-N gold;hydrochloride Chemical compound Cl.[Au] HZYWFQBABNUAAP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
Abstract
The present invention discloses a kind of method of degradation antibiotic, under room temperature, light source irradiation, addition magnetism MIL 101 (Fe)/TiO into the water body containing antibiotic2Material resistant life element is degraded, to magnetic MIL 101 (Fe)/TiO after degradation2Magnetic recovery is carried out, is recycled；101 (Fe)/TiO of magnetism MIL2Composite material be easy to Magnetic Isolation recycling, can recycled for multiple times still keep excellent degradation property, be a kind of environmentally protective environmentally friendly material；And the composite material is prepared simply, and it is easy to operate, energy consumption is saved, catalysis time is short, has high degradation effect for antibiotic under sunlight, has great application prospect in terms of antibiotic of degrading.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a method of degradation antibiotic.
Background technology
In the past few decades, the pollution problem of pharmacy waste water has threatened the ecosystem and the health of the mankind, resists
The abuse of raw element not only results in some undesirable drug responses, but also can cause the drug resistance for germ, will produce super
Grade bacterium.Antibiotic itself has preferable stability, it is difficult to degrade, be discharged into antibiotic in river can enter animal husbandry,
In soil and domestic water, among entering eventually into human body, to influence the health of people.Processing water body moderate resistance at present
The method of raw element it is more classical be advanced oxidation processes, be based on sulphuric acid free radical（SO4 -·）And hydroxyl radical free radical（·OH）Height
Grade oxidation technology has high efficiency for degradation, and in recent years by extensive concern both domestic and external, but advanced oxidation processes are but
Have the shortcomings that apparent, the hydrogen peroxide or persulfate that this technology uses are unable to recycling, and cost consumption is higher, and
Sulfate ion can also cause secondary pollution of water.
TiO2It is widely applied to photocatalytic degradation organic wastewater, it is a kind of semiconductor with good photocatalysis performance
Material, and MIL-101 (Fe) has larger specific surface area and aperture as metal-organic framework materials, is conducive to antibiosis
Element is adsorbed onto its surface and carries out catalytic degradation again, it has certain response also for visible light.TiO2Introducing can effectively subtract
Few photo-generated carrier it is compound, cooperate with the MIL-101 (Fe) to improve performance with this.
Invention content
The purpose of the present invention is to solve the deficiencies in the prior art, it is proposed that a kind of catalyst is convenient for the drop of recycling
The method for solving antibiotic, the catalyst can generate hydroxyl radical free radical and oxygen radical to antibiotic of degrading under visible light,
The method of the present invention is simple to operation, of low cost, is recycled convenient for magnetic recovery, and recycles repeatedly still to have and preferably drop
Effect is solved, avoids causing secondary pollution, is efficient environmentally friendly material.
The present invention provides a kind of method of degradation antibiotic, under room temperature, light source irradiation, into the water body containing antibiotic
Magnetism MIL-101 (Fe)/TiO is added2Material degrades to antibiotic under magnetic agitation as heterogeneous photocatalyst, drops
Antibiotic is solved later to magnetic MIL-101 (Fe)/TiO2Magnetic recovery is carried out, is recycled.
Magnetism MIL-101 (the Fe)/TiO2Preparation method include the following steps：
（1）Prepare MIL-101 (Fe)/TiO2Material, by MIL-101 (Fe)/TiO2Material is in Muffle furnace at 250 ~ 350 DEG C
Constant temperature oxidation 1-10min；
（2）By step（1）Resulting materials strong magnet is adsorbed across pan paper, and magnetic impurity blowout is assigned by no.
A concentration of 5mg/L ~ 35mg/L of antibiotic in the water body.
Magnetic MIL-101 (the Fe)/TiO being added into the water body containing antibiotic2Dosage be 0.1 ~ 1g/L.
The light source is 0 ~ 500W visible lights or sunlight.
The antibiotic is tetracycline, terramycin, aureomycin hydrochloride or Ciprofloxacin.
Compared with the prior art, the present invention has the following advantages and technique effect：
（1）Magnetism MIL-101 (Fe)/TiO provided by the invention2Preparation method it is easy to operate, it is of low cost；
（2）The magnetic material is porous material, preferable adsorptivity is known as antibiosis, convenient for the antibiotic for being adsorbed on surface
Catalytic degradation is carried out, degrading in absorption can be so that degradation constantly carries out；
（3）The heterogeneous catalysis of the present invention is widely applicable to antibiotic non-selectivity；
（4）Catalyst of the present invention recycles convenient for Magnetic Isolation, can still have with repeated recycling utilize, and repeatedly after cycle higher
Degradation effect, non-secondary pollution；
（5）The present invention assigns magnetism of material using heating means, is different from the load Fe for comparing mainstream3O4Advantage be
It is obviously shortened manufacturing cycle, reduces manufacturing cost so that it is simpler to prepare magnetic material, has broad application prospects.
Description of the drawings
Fig. 1 is 1 magnetism MIL-101 (Fe) of the embodiment of the present invention/TiO2Scanning electron microscope (SEM) photograph（SEM）；
Fig. 2 is 1 magnetism MIL-101 (Fe) of the embodiment of the present invention/TiO2X-ray diffractogram（XRD）；
Fig. 3 is 5 magnetism MIL-101 (Fe) of the embodiment of the present invention/TiO2Hysteresis loop figure；
Fig. 4 is 5 magnetism MIL-101 (Fe) of the embodiment of the present invention/TiO2Magneto separate design sketch.
Specific implementation mode
Below by embodiment, invention is further described in detail, but the scope of the present invention be not limited to it is described
Content.
Embodiment 1.
The present embodiment studies magnetism MIL-101 (Fe)/TiO2For the degradation effect of tetracycline, it is as follows：
（1）Magnetic MIL-101 (Fe)/TiO2Preparation：In molar ratio by ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide
1:1:1 is dissolved in 80mLDMF, after stirring in 1 hour, transfers the solution into the anti-of the polytetrafluoroethyllining lining of 100mL
It answers in kettle, reaction kettle is placed in air dry oven, reaction kettle is taken out after reacting 8h at 120 DEG C, reaction kettle is naturally cold
But to room temperature, product taking-up is filtered with sand core funnel after reaction kettle cooling, after being used in combination DMF and ethyl alcohol to flush three times repeatedly
350 DEG C of constant temperature oxidations are put into Muffle furnace after dry 3h at 60 DEG C 5 minutes, then by obtained material strong magnet across title
Paper absorption is measured, no impurity for assigning magnetism is blown out, it is remaining to obtain magnetic MIL-101 (Fe)/TiO2；Obtained magnetism
MIL-101(Fe)/TiO2Scanning electron microscope (SEM) photograph and X-ray diffractogram difference it is as shown in Figure 1, 2；
（2）Using photochemical reactor as simulated visible light light source, light source is 500W nature visible lights, is added into reactor
The tetracycline concentration of 50mL is the aqueous solution of 15mg/L, while 1.0g/L steps being added into reactor（1）Obtained magnetism
MIL-101(Fe)/TiO2, magnetic agitation is carried out in light reaction instrument, is reacted under normal temperature condition, spot sampling point
Analysis.
Control 1：What the material being added in the reactor such as replaced at the quality does not have magnetic MIL-101 (Fe)/TiO2,
His conditional synchronization is rapid（2）.
Control 2：The material being added in the reactor such as replaces at the TiO of quality2, the same step of other conditions（2）.
Removal rate under the conditions of three kinds is as shown in table 1.
Table 1：Absorption degradation effect of the different materials for tetracycline
As shown in Table 1：Magnetic MIL-101 (Fe)/TiO2Degradation effect be significantly stronger than do not have magnetic MIL-101 (Fe)/
TiO2And TiO2。
Embodiment 2
This implementation case research magnetism MIL-101 (Fe)/TiO2To the degradation effect under different antibiotic concentrations, specific steps are such as
Under：
（1）Magnetic MIL-101 (Fe)/TiO2Preparation：In molar ratio by ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide
1:1:In 1 dissolving 80mLDMF, after stirring in 1 hour, the reaction of the polytetrafluoroethyllining lining of 100mL is transferred the solution into
In kettle, reaction kettle is placed in air dry oven, reaction kettle is taken out after reacting 8h at 120 DEG C, by reaction kettle natural cooling
To room temperature, reaction kettle cooling after product taking-up is filtered with sand core funnel, after being used in combination DMF and ethyl alcohol to flush three times repeatedly
350 DEG C of constant temperature oxidations are put into Muffle furnace at 60 DEG C after dry 3h 1 minute, then by obtained material strong magnet across weighing
Paper adsorbs, and assigns magnetic impurity blowout by no, remaining is to obtain magnetic light MIL-101 (Fe)/TiO2；
（2）Using photochemical reactor as simulated visible light light source, light source is 100W nature visible lights, is added into reactor
The tetracycline concentration of 50mL is the aqueous solution of 5mg/L, while 0.1g/L steps being added into reactor（1）Obtained magnetic MIL-
101(Fe)/TiO2, magnetic agitation is carried out in light reaction instrument, is reacted under normal temperature condition, spot sampling analysis.
Into reactor, tetracycline concentration is 15mg/L, the same step of other conditions（2）.
Into reactor, tetracycline concentration is 25mg/L, the same step of other conditions（2）.
Into reactor, tetracycline concentration is 35mg/L, the same step of other conditions（2）.
Table 2：Different tetracycline concentration magnetic MIL-101 (Fe)/TiO2Degradation effect
As shown in Table 2：When other conditions are identical, as tetracycline concentration increases, degradation rate is lower, and has at low concentrations
Better degradation effect.
Embodiment 3
The implementation case research magnetism MIL-101 (Fe)/TiO2Dosage（0.1、0.4、0.7、1.0g/L）Tetracycline is dropped
The influence of solution, is as follows：
（1）Magnetic MIL-101 (Fe)/TiO2Preparation：In molar ratio by ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide
1:1:In 1 dissolving 80mLDMF, after stirring in 1 hour, the reaction of the polytetrafluoroethyllining lining of 100mL is transferred the solution into
In kettle, reaction kettle is placed in air dry oven, reaction kettle is taken out after reacting 8h at 120 DEG C, by reaction kettle natural cooling
To room temperature.Reaction kettle cooling after product taking-up is filtered with sand core funnel, after being used in combination DMF and ethyl alcohol to flush three times repeatedly
250 DEG C of constant temperature oxidations are put into Muffle furnace at 60 DEG C after dry 3h 5 minutes, then by obtained material strong magnet across weighing
Paper adsorbs, and assigns magnetic impurity blowout by no, remaining is to obtain magnetic light MIL-101 (Fe)/TiO2；
（2）Using photochemical reactor as simulated visible light light source, light source is 500W nature visible lights, is added into reactor
The tetracycline concentration of 50mL is the aqueous solution of 25mg/L, while 0.1g/L steps being added into reactor（1）Obtained magnetism
MIL-101(Fe)/TiO2, magnetic agitation is carried out in light reaction instrument, is reacted under normal temperature condition, spot sampling point
Analysis.
0.4g/L steps are added into reactor（1）Obtained magnetic MIL-101 (Fe)/TiO2, other conditions synchronization
Suddenly（2）.
0.7g/L steps are added into reactor（1）Obtained magnetic MIL-101 (Fe)/TiO2, other conditions synchronization
Suddenly（2）.
1.0g/L steps are added into reactor（1）Obtained magnetic MIL-101 (Fe)/TiO2, other conditions synchronization
Suddenly（2）.
Table 3：Magnetic MIL-101 (Fe)/TiO2Influence of the dosage to tetracycline of degrading
As shown in Table 3：At 20 minutes, magnetic MIL-101 (Fe)/TiO2Dosage be 0.1,0.4,0.7,1.0mg/L when pair
The degradation rate of tetracycline is respectively 24.29%, 42.11%, 54.63%, 62.33%, and degradation rate increases as catalyst amount increases
Add, it can be seen that, the degradation rate of tetracycline is directly proportional to catalyst amount.
Embodiment 4
The present embodiment studies influence of the different light sources for tetracycline of degrading, and is as follows：
（1）Magnetic MIL-101 (Fe)/TiO2Preparation：In molar ratio by ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide
1:1:In 1 dissolving 80mLDMF, after stirring in 1 hour, the reaction of the polytetrafluoroethyllining lining of 100mL is transferred the solution into
In kettle, reaction kettle is placed in air dry oven, reaction kettle is taken out after reacting 8h at 120 DEG C, by reaction kettle natural cooling
To room temperature.Reaction kettle cooling after product taking-up is filtered with sand core funnel, after being used in combination DMF and ethyl alcohol to flush three times repeatedly
250 DEG C of constant temperature oxidations are put into Muffle furnace at 60 DEG C after dry 3h 10 minutes, then by obtained material strong magnet across title
Paper absorption is measured, no impurity for assigning magnetism is blown out, it is remaining to obtain magnetic light MIL-101 (Fe)/TiO2；
（2）Using photochemical reactor as simulated visible light light source, do not apply light source, it is dark state to react in instrument, to anti-
The aqueous solution for being added that the tetracycline concentration of 50mL is 25mg/L in device is answered, while 1.0g/L steps being added into reactor（1）
Magnetic MIL-101 (the Fe)/TiO arrived2, magnetic agitation is carried out in light reaction instrument, is reacted under normal temperature condition, is pinpointed
Sampling analysis.
The light source for adjusting reaction instrument is 100W visible lights, the same step of other conditions（2）.
The light source for adjusting reaction instrument is 300W visible lights, the same step of other conditions（2）.
The light source for adjusting reaction instrument is 500W visible lights, the same step of other conditions（2）.
Magnetic stirring apparatus is placed under sunlight and is directly shone, the same step of other conditions（2）.
The degradation rate of 5 kinds of techniques is as shown in table 4.
Table 4：To the degradation effect of tetracycline under different light conditions
As shown in Table 4：Become larger as the intensity of light source increases degradation rate, especially under solar irradiation, due to having ultraviolet light in sunlight,
Catalyst has response for solar irradiation, so degradation rate obviously increases, 20 minutes degradation rates that can reach 90.83%.
Embodiment 5
The implementation case research magnetism MIL-101 (Fe)/TiO2Recycling for degrade tetracycline influence, specific steps
It is as follows：
（1）Magnetic MIL-101 (Fe)/TiO2Preparation：In molar ratio by ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide
1:1:In 1 dissolving 80mLDMF, after stirring in 1 hour, the reaction of the polytetrafluoroethyllining lining of 100mL is transferred the solution into
In kettle, reaction kettle is placed in air dry oven, reaction kettle is taken out after reacting 8h at 120 DEG C, by reaction kettle natural cooling
To room temperature.Reaction kettle cooling after product taking-up is filtered with sand core funnel, after being used in combination DMF and ethyl alcohol to flush three times repeatedly
300 DEG C of constant temperature oxidations are put into Muffle furnace at 60 DEG C after dry 3h 1 minute, then by obtained material strong magnet across weighing
Paper adsorbs, and assigns magnetic impurity blowout by no, remaining is to obtain magnetic light MIL-101 (Fe)/TiO2；
（2）Using photochemical reactor as simulated visible light light source, light source is 500W nature visible lights, is added into reactor
The tetracycline concentration of 50mL is the aqueous solution of 25mg/L, while 1.0g/L steps being added into reactor（1）Obtained magnetism
MIL-101(Fe)/TiO2, magnetic agitation is carried out in light reaction instrument, is reacted under normal temperature condition, spot sampling point
Analysis；
（3）Step（2）After, the catalyst inside reactor is detached with magnetic centrifugal, three are washed repeatedly with hot ethanol and water
It is secondary, input and step after being dried in 100 DEG C of baking ovens（2）The identical reaction system of system in, recycle；Magnetic MIL-
101(Fe)/TiO2Hysteresis loop figure and Magneto separate design sketch distinguish as shown in Figure 3,4, magnetic MIL-101 (Fe)/TiO2Magnetic
Hysteresis line chart and Magneto separate design sketch are as shown in Figure 3,4, as we know from the figure magnetism MIL-101 (Fe)/TiO2It, can be with magnetism
It from solution is kept completely separate out by magnet.
For catalyst by recycling three times, the effect that each cycle degrades to tetracycline is as shown in table 5.
Table 5：Magnetic MIL-101 (Fe)/TiO2It recycles three times and the effect for tetracycline of degrading is compared
As shown in Table 5：After recycling three times, magnetic MIL-101 (Fe)/TiO2It has almost no change for the degradation rate of tetracycline,
Illustrate MIL-101 (Fe)/TiO2Recyclability it is good.
Embodiment 6
The present embodiment studies magnetism MIL-101 (Fe)/TiO2For different antibiotic of degrading（Tetracycline, terramycin, hydrochloric acid gold are mould
Element, Ciprofloxacin）Influence, be as follows：
（1）Magnetic MIL-101 (Fe)/TiO2Preparation：In molar ratio by ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide
1:1:In 1 dissolving 80mLDMF, after stirring in 1 hour, the reaction of the polytetrafluoroethyllining lining of 100mL is transferred the solution into
In kettle, reaction kettle is placed in air dry oven, reaction kettle is taken out after reacting 8h at 120 DEG C, by reaction kettle natural cooling
To room temperature.Reaction kettle cooling after product taking-up is filtered with sand core funnel, after being used in combination DMF and ethyl alcohol to flush three times repeatedly
350 DEG C of constant temperature oxidations are put into Muffle furnace at 60 DEG C after dry 3h 5 minutes, then by obtained material strong magnet across weighing
Paper adsorbs, and assigns magnetic impurity blowout by no, remaining is to obtain magnetic light MIL-101 (Fe)/TiO2；
（2）Using photochemical reactor as simulated visible light light source, light source is 500W nature visible lights, is added into reactor
The tetracycline concentration of 50mL is the aqueous solution of 25mg/L, while 0.5g/L steps being added into reactor（1）Obtained magnetism
MIL-101(Fe)/TiO2, magnetic agitation is carried out in light reaction instrument, is reacted under normal temperature condition, spot sampling point
Analysis.
The aqueous solution of a concentration of 25mg/L of terramycin of 50mL, the same step of other conditions are added into reactor（2）.
The aqueous solution of a concentration of 25mg/L of aureomycin hydrochloride of 50mL, the same step of other conditions are added into reactor（2）.
The Ciprofloxacin Concentration that 50mL is added into reactor is the aqueous solution of 25mg/L, the same step of other conditions（2）.
Each degradation rate is as shown in table 6；
Table 6：Magnetic MIL-101 (Fe)/TiO2Degradation effect comparison to different antibiotic
As shown in Table 6：Magnetic MIL-101 (Fe)/TiO2Degradation for tetracycline, terramycin, aureomycin hydrochloride, Ciprofloxacin
Efficiency is not much different, and illustrates magnetic MIL-101 (Fe)/TiO2For the non-selectivity of Degradation of Antibiotics, can degrade a variety of anti-
Raw element.
Claims (6)
1. a kind of method of degradation antibiotic, which is characterized in that under room temperature, light source irradiation, into the water body containing antibiotic
Magnetism MIL-101 (Fe)/TiO is added2Material resistant life element is degraded, to magnetic MIL-101 (Fe)/TiO after degradation2It carries out
Magnetic recovery recycles.
2. the method for antibiotic of degrading according to claim 1, which is characterized in that magnetism MIL-101 (the Fe)/TiO2's
Preparation method includes the following steps：
（1）Prepare MIL-101 (Fe)/TiO2Material, by MIL-101 (Fe)/TiO2Material is in Muffle furnace at 250 ~ 350 DEG C
Constant temperature oxidation 1-10min；
（2）By step（1）Resulting materials strong magnet is adsorbed across pan paper, and magnetic impurity blowout is assigned by no.
3. the method for antibiotic of degrading according to claim 1, which is characterized in that a concentration of 5mg/ of antibiotic in the water body
L~35mg/L。
4. the method for antibiotic of degrading according to claim 1, which is characterized in that described to add into the water body containing antibiotic
Magnetic MIL-101 (the Fe)/TiO entered2Dosage be 0.1 ~ 1g/L.
5. the method for antibiotic of degrading according to claim 1, which is characterized in that the light source is for 0 ~ 500W visible lights or too
Sunlight.
6. according to claim 1 degrade antibiotic method, which is characterized in that the antibiotic be tetracycline, terramycin,
Aureomycin hydrochloride or Ciprofloxacin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810177551.3A CN108483556A (en) | 2018-03-05 | 2018-03-05 | A method of degradation antibiotic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810177551.3A CN108483556A (en) | 2018-03-05 | 2018-03-05 | A method of degradation antibiotic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108483556A true CN108483556A (en) | 2018-09-04 |
Family
ID=63341376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810177551.3A Pending CN108483556A (en) | 2018-03-05 | 2018-03-05 | A method of degradation antibiotic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108483556A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862120A (en) * | 2019-11-27 | 2020-03-06 | 湖南大学 | Method for treating antibiotic wastewater by utilizing visible light response semiconductor-MOFs hybrid photoelectrocatalysis material electrode |
| CN111185233A (en) * | 2019-12-03 | 2020-05-22 | 青岛大学 | Preparation method and application of heterogeneous Fenton-like catalyst for degrading antibiotics in water environment |
| CN111318260A (en) * | 2020-02-25 | 2020-06-23 | 江苏大学 | TiO22(B) Preparation method and application of/MIL-100 (Fe) composite material |
| CN115337924A (en) * | 2022-08-31 | 2022-11-15 | 江南大学 | Method for efficiently recovering PVA degradation catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012155269A1 (en) * | 2011-05-17 | 2012-11-22 | Frank Gu | Superparamagnetic photocatalytic microparticles |
| CN103657596A (en) * | 2013-12-13 | 2014-03-26 | 天津工业大学 | Synthesis method of magnetic metal organic framework composite material |
| CN104475029A (en) * | 2014-11-11 | 2015-04-01 | 天津工业大学 | Novel preparation and application methods of mesoporous composite material with adsorption and catalytic degradation activity |
| CN105107505A (en) * | 2015-07-02 | 2015-12-02 | 上海应用技术学院 | Magnetic TiO2-porous carbon-Fe3O4 composite visible light photocatalyst and preparation method thereof |
| CN105195096A (en) * | 2015-09-23 | 2015-12-30 | 沈阳药科大学 | Preparation method and application of Fe3O4/MIL-101(Cr) |
| CN105214613A (en) * | 2015-09-23 | 2016-01-06 | 济南大学 | A kind of nucleocapsid structure Fe 3o 4the preparation method of MIL (Fe) composite and application |
| CN107159313A (en) * | 2017-06-14 | 2017-09-15 | 上海应用技术大学 | A kind of core shell structure TiO2The preparation method of nanotube@Ti MOF catalyst |
| CN107285452A (en) * | 2017-06-15 | 2017-10-24 | 昆明理工大学 | A kind of method of fast degradation antibiotic |
-
2018
- 2018-03-05 CN CN201810177551.3A patent/CN108483556A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012155269A1 (en) * | 2011-05-17 | 2012-11-22 | Frank Gu | Superparamagnetic photocatalytic microparticles |
| CN103657596A (en) * | 2013-12-13 | 2014-03-26 | 天津工业大学 | Synthesis method of magnetic metal organic framework composite material |
| CN104475029A (en) * | 2014-11-11 | 2015-04-01 | 天津工业大学 | Novel preparation and application methods of mesoporous composite material with adsorption and catalytic degradation activity |
| CN105107505A (en) * | 2015-07-02 | 2015-12-02 | 上海应用技术学院 | Magnetic TiO2-porous carbon-Fe3O4 composite visible light photocatalyst and preparation method thereof |
| CN105195096A (en) * | 2015-09-23 | 2015-12-30 | 沈阳药科大学 | Preparation method and application of Fe3O4/MIL-101(Cr) |
| CN105214613A (en) * | 2015-09-23 | 2016-01-06 | 济南大学 | A kind of nucleocapsid structure Fe 3o 4the preparation method of MIL (Fe) composite and application |
| CN107159313A (en) * | 2017-06-14 | 2017-09-15 | 上海应用技术大学 | A kind of core shell structure TiO2The preparation method of nanotube@Ti MOF catalyst |
| CN107285452A (en) * | 2017-06-15 | 2017-10-24 | 昆明理工大学 | A kind of method of fast degradation antibiotic |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862120A (en) * | 2019-11-27 | 2020-03-06 | 湖南大学 | Method for treating antibiotic wastewater by utilizing visible light response semiconductor-MOFs hybrid photoelectrocatalysis material electrode |
| CN110862120B (en) * | 2019-11-27 | 2021-07-20 | 湖南大学 | Method for treating antibiotic wastewater by utilizing visible light response semiconductor-MOFs hybrid photoelectrocatalysis material electrode |
| CN111185233A (en) * | 2019-12-03 | 2020-05-22 | 青岛大学 | Preparation method and application of heterogeneous Fenton-like catalyst for degrading antibiotics in water environment |
| CN111185233B (en) * | 2019-12-03 | 2023-10-10 | 青岛大学 | Preparation method and application of heterogeneous Fenton-like catalyst for degrading antibiotics in water environment |
| CN111318260A (en) * | 2020-02-25 | 2020-06-23 | 江苏大学 | TiO22(B) Preparation method and application of/MIL-100 (Fe) composite material |
| CN115337924A (en) * | 2022-08-31 | 2022-11-15 | 江南大学 | Method for efficiently recovering PVA degradation catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zeng et al. | Visible-light-driven sonophotocatalysis and peroxymonosulfate activation over 3D urchin-like MoS2/C nanoparticles for accelerating levofloxacin elimination: Optimization and kinetic study | |
| CN106732524B (en) | Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof | |
| CN108483556A (en) | A method of degradation antibiotic | |
| CN107285452B (en) | Method for rapidly degrading antibiotics | |
| Ammar et al. | Synthesis, characterization and environmental remediation applications of polyoxometalates-based magnetic zinc oxide nanocomposites (Fe3O4@ ZnO/PMOs) | |
| CN107362805B (en) | Preparation method and application of magnetic bismuth oxide composite photocatalyst based on biomass charcoal | |
| CN106732735A (en) | A kind of composite of photocatalytic degradation Microcystin and preparation method and application | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN108212192A (en) | A kind of light-fenton catalyst and preparation method thereof | |
| CN109847786A (en) | A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H | |
| CN109806900B (en) | Molecular imprinting type Ag/Ag3VO4Preparation method and application of/CN nanosheet composite photocatalyst | |
| CN109261172A (en) | A kind of preparation method and purposes of bismuth oxyiodide/bismuth oxybromide heterojunction photocatalyst | |
| CN106881111A (en) | Composite bismuth vanadium photocatalyst of cuprous oxide and silver-colored mutual load and its preparation method and application | |
| CN108355720A (en) | A kind of ferroso-ferric oxide@rGO@MIL-100 (Fe) light-fenton catalysts and its preparation and application | |
| CN109847803A (en) | A kind of defect MOF catalyst and the preparation method and application thereof | |
| CN110756163A (en) | Nano CoFe2O4Carbon fiber felt composite material and preparation method and application thereof | |
| CN111686770B (en) | Metal ion co-doped BiOBr microsphere, preparation method and application thereof | |
| Zhu et al. | Flower-like bentonite-based Co3O4 with oxygen vacancies-rich as highly efficient peroxymonosulfate activator for lomefloxacin hydrochloride degradation | |
| CN110841669B (en) | Method for treating heavy metals and organic pollutants by using zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst | |
| Cao et al. | Reductive removal of Cr (VI) by citric acid promoted by ceramsite particles: Kinetics, influential factors, and mechanisms | |
| CN105597793B (en) | A kind of photochemical catalyst and its preparation method and application | |
| Li et al. | Synthesis of recyclable magnetic mesoporous RH-FSBA photoelectrocatalyst with double cavity structure | |
| CN105879890B (en) | Magnetic composite photocatalyst and its preparation method and application | |
| CN109499591B (en) | Preparation method and application of magnetically-recoverable photo-Fenton-like catalyst | |
| CN107008333A (en) | Magnetic heterogeneous light Fenton NiFe2O4The preparation method of/ZnO composite nano materials and the application of the material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180904 |
|
| RJ01 | Rejection of invention patent application after publication |