CN107285452A - A kind of method of fast degradation antibiotic - Google Patents

A kind of method of fast degradation antibiotic Download PDF

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Publication number
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
tio
reactor
organic framework
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CN107285452B (en
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陕绍云
何磊
贾庆明
蒋丽红
王亚明
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Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691Coordination polymers, e.g. metal-organic frameworks [MOF]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38Catalysts 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343Nature 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 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

A kind of method of fast degradation antibiotic
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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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
CN110483788A (en) * 2019-07-19 2019-11-22 中国地质大学(武汉) A kind of MIL-53(Fe) composite material and preparation method and the application for tetracycline of degrading
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
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
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