CN107285452A - A kind of method of fast degradation antibiotic - Google Patents
A kind of method of fast degradation antibiotic Download PDFInfo
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- CN107285452A CN107285452A CN201710450226.5A CN201710450226A CN107285452A CN 107285452 A CN107285452 A CN 107285452A CN 201710450226 A CN201710450226 A CN 201710450226A CN 107285452 A CN107285452 A CN 107285452A
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- antibiotic
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- reactor
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 43
- 230000015556 catabolic process Effects 0.000 title claims abstract description 42
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000003918 potentiometric titration Methods 0.000 claims abstract description 5
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 54
- 239000004098 Tetracycline Substances 0.000 claims description 43
- 235000019364 tetracycline Nutrition 0.000 claims description 43
- 150000003522 tetracyclines Chemical class 0.000 claims description 43
- 239000012924 metal-organic framework composite Substances 0.000 claims description 35
- 229960002180 tetracycline Drugs 0.000 claims description 32
- 229930101283 tetracycline Natural products 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 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 6
- 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 6
- 229940063650 terramycin Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 5
- 239000013384 organic framework Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000004408 titanium dioxide Substances 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
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 26
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 19
- 235000019394 potassium persulphate Nutrition 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000013177 MIL-101 Substances 0.000 description 11
- 229940040944 tetracyclines Drugs 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 7
- 238000006552 photochemical reaction Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- -1 sulphuric acid free radical Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000003321 amplification 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 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
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000002023 wood Substances 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
- 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
Landscapes
- 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 kind of method of fast degradation antibiotic；This method is with MIL 101 (Fe)/TiO2Composite as catalyst, under normal temperature weak light source can very big catalytic activation persulfate, quickly produce a large amount of potentiometric titrations degraded antibiotic；The composite is easily recycled, and preferable activation effect is still kept after can repeatedly using, and is a kind of environmentally friendly material of environmental protection；It is easy to operate and this method equipment is simple, energy consumption is saved, catalysis time is short, the not enough area of illumination serious for haze there can be high degradation effect under weaker natural light for antibiotic, have great application prospect in terms of antibiotic of degrading.
Description
Technical field
The invention belongs to pharmacy wastewater treatment technical field, and in particular to one kind is based on MIL-101 (Fe)/TiO2Composite wood
The method for expecting to activate persulfate fast degradation antibiotic under weak light source.
Background technology
China is antibiotic usage big country, the antibiosis among also result in water pollution, rivers while disease is treated
Element is mainly derived from pharmacy waste water, aquaculture waste water and animal wastes etc., and antibiotic is difficult to degraded under natural light causes anti-
The continuous cumulative rises of raw element concentration, the intake of antibiotic can cause humans and animals to develop immunity to drugs, and produce superbacteria, influence people
Class and the health of animal.
At present mainly there be the method for antibiotic in processing water body：The side such as absorption, catalytic degradation, UF membrane and biological treatment
Method.Based on sulphuric acid free radical（SO4 -·）High-level oxidation technology there is high efficiency for degraded, in recent years by both domestic and external wide
General concern, persulfate（S2O8 2-）SO can be produced by the activation such as ultraviolet light, heat, ultrasound or transition metal4 -·.Transition gold
Although belonging to, ion is more cheap compared with other active mode costs, if directly applying metal ion in water body, it has
Certain toxicity, can produce secondary pollution and can not recycle again, therefore people are more likely to research heterogeneous catalysis to live
Change persulfate.And metal organic framework composite is as heterogeneous catalysis, due to its stability in water, it is to avoid
For the secondary pollution of water body, again can multiple Reusability, be a kind of environmentally friendly new material, as Now Domestic outside
Study hotspot.
Metal organic framework composite is that certain chemical substance is loaded on metal-organic framework materials, and metal is organic
Framework material is the orderly network structure being bonded by organic ligand and inorganic metal ion.Metal-organic framework materials exist
There is highest specific surface area, minimum crystalline density and adjustable hole size and functional structure at present, other are easily loaded
Material is without changing self structure, and metal-organic framework materials contain substantial amounts of unsatuated metal site, use it
Make some special applications：Absorption, separation, catalysis etc..
Photochemical catalyst has great dependence for the intensity of light source, and dim light can reduce its efficiency for degraded, for
The seriously polluted area of some antibiotic, often also has serious haze for a long time, and illumination is not enough, and degradation rate is slower, if improving
Degradation rate needs to apply light source generation energy consumption again again；Although advanced oxidation processes independent of with intensity of illumination, according to current
The degradation rate of document report, half an hour degradation rate is below 90%, although time-consuming major part photochemical catalyst has remarkable improvement,
But it is still undesirable.The present invention is by based on metal organic framework composite MIL-101 (Fe)/TiO2Activate persulfuric acid
Salt, significantly improves degradation efficiency, can reach within ten minutes 93% Degradation of Antibiotics rate, for antibiotic treatment provide it is wide before
Scape.
The content of the invention
The invention aims to solve the deficiencies in the prior art, it is proposed that a kind of method of fast degradation antibiotic,
This method utilizes MIL-101 (Fe)/TiO2Composite activates persulfate under weak light source, produces the sulfuric acid of a large amount of oxidisability
Antibiotic in free radical, the further oxidative degradation water body of sulphuric acid free radical；I.e. under normal temperature, weak light source, to containing antibiotic
Persulfate is added in water body as oxidant, while using metal organic framework composite as heterogeneous catalysis, plus
Enter metal organic framework composite and efficiently activate persulfate quickly to produce potentiometric titrations, potentiometric titrations are to water body
In organic pollution antibiotic degraded, so as to improve water quality.
The metal organic framework composite is MIL-101 (Fe)/TiO2。
Metal organic framework composite MIL-101 (the Fe)/TiO2Preparation method comprise the following steps：
（1）It is 1 by the mol ratio of ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide:2:3~3:2:1 ratio, by raw material
It is dissolved in DMF, is sufficiently stirred for after 1 ~ 2 hour, the solution stirred is transferred in the reactor of polytetrafluoroethyllining lining,
Reactor is positioned in air dry oven, reactor is taken out after reacting 2 ~ 24h at 120 ~ 160 DEG C, reactor is naturally cold
But room temperature is arrived；
（2）Suction filtration product after the cooling of question response kettle, and vacuumized at 60 ~ 80 DEG C after being flushed three times successively with DMF and ethanol
Dry 12 ~ 24h；Obtain metal organic framework composite MIL-101 (Fe)/TiO2。
The persulfate includes one kind or any than several in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate.
The mol ratio of antibiotic is 10 in the persulfate added into water body and water body:1~40:1.
Metal organic framework composite MIL-101 (the Fe)/TiO2Dosage be 0.1 ~ 2g/L.
The weak light source is 0 ~ 500W visible rays.
Described metal organic framework composite MIL-101 (Fe)/TiO2Recycled for multiple times can be passed through, gold is embodied
Belong to organic framework composite material MIL-101 (Fe)/TiO2Maximum catalytic capability.
The antibiotic is tetracycline, terramycin or aureomycin hydrochloride.
The present invention has advantages below and technique effect compared with prior art：
（1）Metal organic framework composite MIL-101 (Fe)/TiO that the present invention is provided2Preparation method it is simple to operate, energy
Consumption is relatively low, cheap；
（2）The metal organic framework composite is porous material, with unsatuated metal activated centre, enhances persulfate
The effect of sulphuric acid free radical is produced, degradation effect of the catalyst for antibiotic is improved；
（3）The heterogeneous catalysis of the present invention is widely applicable to antibiotic non-selectivity；
（4）Catalyst of the present invention can be utilized with repetitive cycling, non-secondary pollution；
（5）Present invention may apply to play more preferable degradation effect under weak light source, have more significant for the not enough area of illumination
Fast degradation effect；
（6）The method of the present invention need not consume additional energy, including ultrasound, intense light source, heat and electricity etc., reduce cost, have
Have broad application prospects.
Brief description of the drawings
Fig. 1 is metal-organic framework materials MIL-101 (Fe)/TiO2Scanning electron microscope (SEM) photograph（SEM）, wherein A figures, B figures are
Different amplification.
Embodiment
The present invention is described in further detail below by embodiment, but the scope of the present invention be not limited to it is described
Content.
The present invention is using tetracycline as typical antibiotic, in order to prove non-selectivity of the present invention to target contaminant,
Terramycin and aureomycin hydrochloride be have selected as target antibiotic.
Embodiment 1：The method particular content of this fast degradation antibiotic is as follows：
The present embodiment is with 12h/120 DEG C of MIL-101 (the Fe)/TiO prepared for preparation condition2Catalyst, studies MIL-101
(Fe)/TiO2For the degradation effect of tetracycline；
（1）Metal organic framework composite MIL-101 (Fe)/TiO2Preparation：By ferric chloride (FeCl36H2O), terephthalic acid (TPA) and
Titanium dioxide in molar ratio 1:1:1 is dissolved in 40mLDMF, after the stirring of 1 hour, transfers the solution into the poly- of 100mL
In the reactor of tetrafluoroethene liner, reactor is placed in air dry oven, is reacted at 120 DEG C and reaction is taken out after 12h
Kettle, room temperature is naturally cooled to by reactor.Product taking-up is subjected to suction filtration with sand core funnel after reactor cooling, and with DMF with
Ethanol vacuumizes dry 12h after flushing three times repeatedly at 60 DEG C；Produce metal organic framework composite MIL-101 (Fe)/
TiO2。
Obtained metal organic framework composite MIL-101 (Fe)/TiO2Scanning electron microscope (SEM) photograph it is as shown in Figure 1.
（2）Using photochemical reaction instrument as simulated visible light light source, light source is the natural visible rays of 300W, into reactor
It is 20 to add mol ratio:1 potassium peroxydisulfate and tetracycline, keeps the 80mg/L Fourth Rings that liquor capacity is 50mL in reactor
Plain solution, while toward adding 50mg MIL-101 (Fe)/TiO in reactor2Magnetic agitation is carried out in light reaction instrument, normal
Reacted under the conditions of temperature, spot sampling analysis；
Compare technique 1：Metal organic framework composite MIL-101 (Fe)/TiO is added without in the reactor2, other conditions are same
Step（2）；
Compare technique 2：Potassium peroxydisulfate, the same step of other conditions are added without in the reactor（2）；
The clearance of three kinds of techniques is as shown in table 1.
Table 1：Metal organic framework composite MIL-101 (Fe)/TiO2For the absorption degradation effect of tetracycline
As shown in Table 1：Metal organic framework composite MIL-101 (Fe)/TiO is used alone2Or potassium peroxydisulfate is for Fourth Ring
The removal effect of element is not obvious, but ought add metal organic framework composite MIL-101 (Fe)/TiO simultaneously2And potassium peroxydisulfate
When, the clearance of tetracycline is substantially lifted rapidly.
Embodiment 2：The present embodiment is with MIL-101 (Fe)/TiO of 12h/120 DEG C of preparation condition preparation2For catalysis
Agent, research potassium peroxydisulfate is different with the mol ratio of tetracycline（N potassium peroxydisulfates/n tetracycline=10,20,30,40）Lived for catalysis
Change the influence of reaction；
（1）Step in the preparation method be the same as Example 1 of metal organic framework composite（1）；
（2）Using photochemical reaction instrument as simulated visible light light source, light source is the natural visible rays of 300W, is added into reactor
Mol ratio is 10:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor molten for 50mL 80mg/L tetracyclines
Liquid, while toward adding 50mg MIL-101 (Fe)/TiO in reactor2Magnetic agitation is carried out in light reaction instrument, in normal temperature
Under the conditions of reacted, spot sampling analysis；
（3）It is 20 that mol ratio is added into reactor:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor
For 50mL 80mg/L tetracyclines, the same step of other conditions（2）；
（4）It is 30 that mol ratio is added into reactor:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor
For 50mL 80mg/L tetracyclines, the same step of other conditions（2）；
（5）It is 40 that mol ratio is added into reactor:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor
For 50mL 80mg/L tetracyclines, the same step of other conditions（2）.
Four kinds of technique clearances are as shown in table 2.
Table 2：Different n potassium peroxydisulfates/n tetracyclines input amounts are than the comparison for tetracycline degradation effect
As shown in Table 2：With n potassium peroxydisulfates/n tetracyclines ratio increase, ascendant trend is presented in reaction degradation rate, but works as ratio
20:After 1, less, from the aspect of reaction efficiency and cost, n potassium peroxydisulfates/n tetracycline=20 are most for the change of degradation rate
Excellent condition.
Embodiment 3：The implementation case is MIL-101 (the Fe)/TiO prepared with 12h/120 DEG C of preparation condition2For catalysis
Agent, research MIL-101 (Fe)/TiO2Dosage（5mg、25mg、50mg、75mg、100mg）The shadow reacted for catalytic activation
Ring
（1）Metal organic framework composite MIL-101 (Fe)/TiO2Preparation method with the step in case study on implementation 1（1）；
（2）Using photochemical reaction instrument as simulated visible light light source, light source is the natural visible rays of 300W, is added into reactor
Mol ratio is 20:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor molten for 50mL 80mg/L tetracyclines
Liquid, while magnetic agitation is carried out in light reaction instrument toward addition 5mg MIL-101 (Fe)/TiO2 in reactor, in normal temperature bar
Reacted under part, spot sampling analysis；
（3）25mg MIL-101 (Fe)/TiO is added into reactor2, the same step of other conditions（2）；
（4）50mg MIL-101 (Fe)/TiO is added into reactor2, the same step of other conditions（2）；
（5）75mg MIL-101 (Fe)/TiO is added into reactor2, the same step of other conditions（2）；
（6）100mg MIL-101 (Fe)/TiO is added into reactor2, the same step of other conditions（2）；
The degradation rate of five kinds of techniques is as shown in table 3 below；
Table 3：Different metal organic framework composite material MIL-101 (Fe)/TiO2Effect of the dosage to tetracycline of degrading
As shown in Table 3：At 20 minutes, MIL-101 (Fe)/TiO2Dosage be 5mg, 25mg, 50mg, 75mg, 100mg when
Degradation rate to tetracycline is respectively 70.3%, 88.2%, 93.4%, 89.8%, 89.3%.There is this visible, with catalyst amountses
Increasing, degradation rate rose before this, and downward trend is presented after catalyst amountses reach 50mg, MIL-101 (Fe)/
TiO2, it is optimal conditions when dosage is 50mg to tetracycline degradation effect preferably.
Embodiment 4：The present embodiment is the different preparation times of research（2、12、24h）Or temperature（120、140、160℃）Gold
The influence that category organic framework composite material is reacted for catalytic activation
（1）Metal organic framework composite MIL-101 (Fe)/TiO of different preparation times2Preparation：By six water tri-chlorinations
Iron, terephthalic acid (TPA) and titanium dioxide in molar ratio 1:2:3 are dissolved in 80mLDMF, after the stirring of 2 hours, by solution
In the reactor for being transferred to 100mL polytetrafluoroethyllining lining, reactor is placed in air dry oven, divided at 120 DEG C
Not Fan Ying 2,12, take out reactor after 24h, reactor is naturally cooled into room temperature；By product taking-up sand after reactor cooling
Core funnel carries out suction filtration, and dry 24h is vacuumized at 80 DEG C after being flushed three times repeatedly with DMF and ethanol；Obtain the gold
Belong to organic framework composite material MIL-101 (Fe)/TiO2；
（2）Metal organic framework composite MIL-101 (Fe)/TiO of different preparation temperatures2Preparation：By six water tri-chlorinations
Iron, terephthalic acid (TPA) and titanium dioxide in molar ratio 3:2:1 is dissolved in 40mLDMF, after the stirring of 2 hours, by solution
In the reactor for being transferred to 100mL polytetrafluoroethyllining lining, reactor is placed in air dry oven, 140 DEG C, 160
Reactor is taken out after reacting 12h at DEG C, reactor is naturally cooled into room temperature；Product taking-up core is leaked after reactor cooling
Bucket carries out suction filtration, and dry 24h is vacuumized at 80 DEG C after being flushed three times repeatedly with DMF and ethanol；Obtaining the metal has
Machine skeletal composite MIL-101 (Fe)/TiO2；
（3）Using photochemical reaction instrument as simulated visible light light source, light source is the natural visible rays of 300W, is added into reactor
Mol ratio is 20:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor molten for 50mL 80mg/L tetracyclines
Liquid, while toward adding MIL-101 (Fe)/TiO for being prepared under the conditions of 50mg 2h/120 DEG C in reactor2, in light reaction instrument
Middle carry out magnetic agitation, is reacted under normal temperature condition, spot sampling analysis；
（4）MIL-101 (the Fe)/TiO prepared under the conditions of 50mg 12h/120 DEG C is added into reactor2, other conditions synchronization
Suddenly（3）；
（5）MIL-101 (the Fe)/TiO prepared under the conditions of 50mg 24h/120 DEG C is added into reactor2, other conditions synchronization
Suddenly（3）；
（6）MIL-101 (the Fe)/TiO prepared under the conditions of 50mg 12h/140 DEG C is added into reactor2, other conditions synchronization
Suddenly（3）；
（7）MIL-101 (the Fe)/TiO prepared under the conditions of 50mg 12h/160 DEG C is added into reactor2, other conditions synchronization
Suddenly（3）；
The degradation rate for metallic framework composite MIL-101 (Fe)/TiO2 that five kinds of techniques are obtained is as shown in table 4.
Table 4：Metal organic framework composite MIL-101 (the Fe)/TiO prepared under different time or temperature conditionss2It is right
The degradation effect of tetracycline
As shown in Table 4：After 20 minutes, under 12h preparation times, optimal preparation temperature is 120 DEG C, as temperature is raised, drop
Solution rate have dropped on the contrary.Under 120 DEG C of reaction temperature, the peak optimization reaction time is 12h.
Embodiment 5：The present embodiment is the metal organic framework composite MIL- prepared with 12h/120 DEG C of preparation condition
101(Fe)/TiO2For catalyst, influence of the different intensities of light source for tetracycline of degrading is studied；
（1）Metal organic framework composite MIL-101 (Fe)/TiO2Preparation method with the step in case 1（1）；
（2）Using photochemical reaction instrument as simulated visible light light source, do not apply light source, be dark state in reaction instrument, to anti-
It is 20 to answer and mol ratio is added in device:1 potassium peroxydisulfate and tetracycline, it is 50mL's to keep liquor capacity in reactor
80mg/L tetracyclines, while toward adding 50mg MIL-101 (Fe)/TiO in reactor2Magnetic is carried out in light reaction instrument
Power is stirred, and is reacted under normal temperature condition, spot sampling analysis；
（3）The light source of regulation reaction instrument is 100W visible rays, and other conditions are same（2）；
（4）The light source of regulation reaction instrument is 300W visible rays, and other conditions are same（2）；
（5）The light source of regulation reaction instrument is 500W visible rays, and other conditions are same（2）；
The degradation rate of four kinds of techniques is as shown in table 5.
Table 5：To the degradation effect of tetracycline under the conditions of the different intensities of light source
As shown in Table 5：In 100W and 300W compared with that can have most degradation rate under weak light source, strong light is helpless to improve degradation efficiency.
Embodiment 6：The implementation case is MIL-101 (the Fe)/TiO prepared with 12h/120 DEG C of preparation condition2For catalysis
Agent, research MIL-101 (Fe)/TiO2Recycling for degrade tetracycline influence.
（1）Metal organic framework composite MIL-101 (Fe)/TiO2Preparation method with the step in case 1（1）；
（2）Using photochemical reaction instrument as simulated visible light light source, light source is the natural visible rays of 300W, is added into reactor
Mol ratio is 20:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor molten for 50mL 80mg/L tetracyclines
Liquid, while toward adding 50mg MIL-101 (Fe)/TiO in reactor2Magnetic agitation is carried out in light reaction instrument, in normal temperature bar
Reacted under part, spot sampling analysis；
（3）Step（2）After end, the catalyst inside reactor is centrifuged at a high speed, put into after being dried in 100 DEG C of baking ovens
With step（2）System identical reaction system in, recycle；
Catalyst is by four recyclings, and the result that each circulation is degraded to tetracycline is as shown in table 6；
Table 6：MIL-101(Fe)/TiO2Four circulations are compared for the effect for tetracycline of degrading
As shown in Table 6：After four circulations, and in the case where catalyst is lossy, metal organic framework composite MIL-101
(Fe)/TiO2More than 90% is still maintained at for the degradation rate for tetracycline of degrading, illustrates MIL-101 (Fe)/TiO2It is recyclable
Property is good.
Embodiment 7：The present embodiment is MIL-101 (the Fe)/TiO prepared with 12h/120 DEG C of preparation condition2For catalyst,
Study MIL-101 (Fe)/TiO2For different antibiotic of degrading（Tetracycline, terramycin, aureomycin hydrochloride）Influence；
（1）Metal organic framework composite MIL-101 (Fe)/TiO2Preparation method with the step in case 1（1）；
（2）Using photochemical reaction instrument as simulated visible light light source, light source is the natural visible rays of 300W, is added into reactor
Mol ratio is 20:1 potassium peroxydisulfate and tetracycline, keeps liquor capacity in reactor molten for 50mL 80mg/L tetracyclines
Liquid, while toward adding 50mg MIL-101 (Fe)/TiO in reactor2Magnetic agitation is carried out in light reaction instrument, in normal temperature bar
Reacted under part, spot sampling analysis；
（3）50mL 80mg/L terramycin solution is added into reactor, other conditions are same（2）；
（4）50mL 80mg/L aureomycin hydrochloride solution is added into reactor, other conditions are same（2）；
The degradation rate of three kinds of techniques is as shown in table 7；
Table 7：MIL-101(Fe)/TiO2Degradation effect contrast to different antibiotic
As shown in Table 7：After 20 minutes, MIL-101 (Fe)/TiO2For tetracycline, terramycin, aureomycin hydrochloride degraded
Efficiency is more or less the same, and illustrates MIL-101 (Fe)/TiO2For the non-selectivity of Degradation of Antibiotics, can degrade Multiple Classes of Antibiotics.
Claims (7)
1. a kind of method of fast degradation antibiotic, it is characterised in that：Under normal temperature, weak light source, to the water body containing antibiotic
Middle addition persulfate is as oxidant, while using metal organic framework composite as heterogeneous catalysis, adding gold
Category organic framework composite material efficiently activates persulfate and quickly produces potentiometric titrations, and potentiometric titrations are in water body
Organic pollution antibiotic is degraded, so as to improve water quality.
2. the method for fast degradation antibiotic according to claim 1, it is characterised in that：Metal organic framework composite
For MIL-101 (Fe)/TiO2。
3. the method for fast degradation antibiotic according to claim 2, it is characterised in that metal organic framework composite
For MIL-101 (Fe)/TiO2Preparation method it is as follows：
（1）It is 1 by the mol ratio of ferric chloride (FeCl36H2O), terephthalic acid (TPA) and titanium dioxide:2:3~3:2:1 ratio, by raw material
It is dissolved in DMF, is sufficiently stirred for after 1 ~ 2 hour, the solution stirred is transferred in the reactor of polytetrafluoroethyllining lining,
Reactor is positioned in air dry oven, reactor is taken out after reacting 2 ~ 24h at 120 ~ 160 DEG C, reactor is naturally cold
But room temperature is arrived；
（2）Suction filtration product after the cooling of question response kettle, and vacuumized at 60 ~ 80 DEG C after being flushed three times successively with DMF and ethanol
Dry；Produce metal organic framework composite MIL-101 (Fe)/TiO2。
4. the method for fast degradation antibiotic according to claim 1, it is characterised in that：Persulfate includes persulfuric acid
One or more in potassium, sodium peroxydisulfate, ammonium persulfate.
5. the method for fast degradation antibiotic according to claim 1, it is characterised in that：The persulfuric acid added into water body
The mol ratio of antibiotic is 10 in salt and water body:1~40:1, metal organic framework composite MIL-101 (Fe)/TiO2Throwing
Dosage is 0.1 ~ 2g/L.
6. the method for the fast degradation antibiotic according to right 1, it is characterised in that：Weak light source is 0 ~ 500W visible rays.
7. the method for the fast degradation antibiotic according to right 1, it is characterised in that：Antibiotic be tetracycline, terramycin or
Aureomycin hydrochloride.
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| CN108483556A (en) * | 2018-03-05 | 2018-09-04 | 昆明理工大学 | A method of degradation antibiotic |
| CN108529720A (en) * | 2018-03-22 | 2018-09-14 | 华南师范大学 | A kind of mosaic electrode and its preparation method and application |
| CN108911009A (en) * | 2018-07-24 | 2018-11-30 | 湖南大学 | Utilize the method for antibiotic in nickel doping metals organic framework material removal water body |
| CN109758714A (en) * | 2019-01-23 | 2019-05-17 | 浙江理工大学 | A method of repairing antibiotic contaminated soil |
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| CN108529720B (en) * | 2018-03-22 | 2021-06-29 | 华南师范大学 | Particle electrode and preparation method and application thereof |
| CN108529720A (en) * | 2018-03-22 | 2018-09-14 | 华南师范大学 | A kind of mosaic electrode and its preparation method and application |
| CN108911009A (en) * | 2018-07-24 | 2018-11-30 | 湖南大学 | Utilize the method for antibiotic in nickel doping metals organic framework material removal water body |
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| 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 |
| CN111530501A (en) * | 2020-05-08 | 2020-08-14 | 五邑大学 | Fe/Zn-MOF derived magnetic photocatalytic material and preparation method and application thereof |
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