CN106430516B - A method of antibacterials in single persulfate degradation water are activated based on the order mesoporous cobaltosic oxide of Fe2O3 doping - Google Patents
A method of antibacterials in single persulfate degradation water are activated based on the order mesoporous cobaltosic oxide of Fe2O3 doping Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 14
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 11
- 230000015556 catabolic process Effects 0.000 title claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 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 abstract description 86
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 67
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 230000005389 magnetism Effects 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007605 air drying Methods 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 3
- 229940124350 antibacterial drug Drugs 0.000 abstract 1
- 229910001429 cobalt ion Inorganic materials 0.000 abstract 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- -1 iron ion Chemical class 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 208000031295 Animal disease Diseases 0.000 description 1
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000007660 quinolones Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a kind of methods for activating antibacterials in single persulfate degradation water based on the order mesoporous cobaltosic oxide of Fe2O3 doping, realize especially by following steps: preparation TOM-Co3O4；Prepare magnetism TOM-Co3O4/CoFe2O4；By magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed, is transferred in brown shaking flask with the aqueous solution containing antibacterials；Add single persulfate；Magnetism TOM-Co is separated by externally-applied magnetic field3O4/CoFe2O4.Using the method for the invention, the removal rate of Exemplary antibacterial drug Ciprofloxacin is more than 95% in 60min；Cobalt ions and iron ion dissolution rate are extremely low, reduce environmental pollution；Catalyst is separable to be reused, and operating cost is reduced.
Description
Technical field
The invention belongs to technical field of sewage, and in particular to emerging organic pollutant and organic contamination difficult to degrade in water
The processing method of object, more particularly to a kind of activated in single persulfate degradation water based on the order mesoporous cobaltosic oxide of Fe2O3 doping are resisted
The method of bacterium drug.
Background technique
In recent years, drug and personal-care supplies (Pharmaceuticals and Personal Care Products,
PPCPs a kind of emerging environmental contaminants) are had become, are detected in the surrounding mediums such as underground water, surface water, soil,
And it is proved to cause environment and human health certain harm.Ciprofloxacin (Ciprofloxacin, CIP) belongs to quinolone
Class antibacterials are widely used in the treatment of the mankind and Animal diseases.After remaining Ciprofloxacin enters human body, human body can be generated
Toxic side effect, and greatly enhance the drug resistance of human body pathogen.On the other hand, after animal has taken in a large amount of Ciprofloxacins, with excrement
Urine excretes, and enters in natural environment, constitutes to the ecosystem potentially hazardous.Ciprofloxacin is total as a kind of people and animals
Medication, medicament residue are bigger to human health damage by food chain.It is dropped studies have pointed out that Ciprofloxacin is more difficult by microorganism
Solution, and cannot be effectively removed by conventional water treatment process.Therefore, it needs to find the dirt that effective ways solve Ciprofloxacin in environment
Dye problem.
In recent years, it is based on potentiometric titrations (SO4 -) high-level oxidation technology receive the extensive concern of researcher.
Wherein transition metal ions activates single persulfate (Peroxymonosufate, PMS) system to generate Strong oxdiative active
SO4 -It efficient can carry out at room temperature, without external energy (ultrasound, heat source and light source), before wide application
Scape.But the problems such as homogeneous list persulfate catalyst system recycles difficulty and easily causes raw secondary environmental pollution there are catalyst.
Summary of the invention
The present invention provides one kind to form magnetic TOM-Co based on the order mesoporous cobaltosic oxide of Fe2O3 doping3O4/CoFe2O4
The method for activating antibacterials in single persulfate degradation water, it is intended to solve catalyst in homogeneous single persulfate activation systems
The problem of (transition metal ions) recycles difficulty and easily causes secondary environmental pollution；Solve currently used heterogeneous spinelle
Type specific surface area of catalyst is small, the lower problem of catalytic capability；And heterogeneous TOM-Co3O4It activates in single persulfate system
The problem of catalyst reclaimer operation complexity.
A method of antibacterials in single persulfate degradation water are activated based on the order mesoporous cobaltosic oxide of Fe2O3 doping,
It sequentially includes the following steps:
One, TOM-Co is prepared3O4:
Co (NO is added to after template KIT-6 is fully ground3)2·6H2In the ethanol solution of O, at room temperature
It stirs 1 h and obtains solution A；
By step 1Acquired solution A forced air drying under the conditions of 60 DEG C obtains pink solid powder, this is consolidated
Body powder is transferred in crucible, and places it in 5 h of roast, the heating of the Muffle furnace under the conditions of 200 DEG C in Muffle furnace
Speed is 2 DEG C/min；
By step 1Brown solid powder after middle roast is added to Co (NO after being fully ground3)2·6H2The second of O
In alcoholic solution, 1 h is stirred at room temperature and obtains solution B；
By step 1Acquired solution B forced air drying under the conditions of 60 DEG C obtains black solid, this solid is shifted
To crucible, and 5 h of roast under the conditions of 450 DEG C being placed it in Muffle furnace, the heating rate of the Muffle furnace is 2 DEG C/
min；
By step 1The black solid powder of middle roast is cooled to room temperature, and is added after being fully ground to filling 2
In the round-bottomed flask of mol/L NaOH solution, 12 h are stirred under 60 DEG C of water bath conditions, by 30 min of solution left standstill after stirring
Supernatant is removed, above step is in triplicate；
By step 1Products obtained therefrom spends ultrapure water respectively and ethyl alcohol is cleaned to pH=7 repeatedly, 60 DEG C of conditions
It is fully ground to obtain TOM-Co again after lower vacuum drying3O4；
Two, magnetism TOM-Co is prepared3O4/CoFe2O4:
By TOM-Co3O4It is added to Fe (NO3)3·9H2In O- ethanol solution, 1 h is stirred at room temperature；
Preferably, step 2Described in TOM-Co3O4、Fe(NO3)3·9H2The molar ratio of O is 1:1；
Preferably, step 2Described in Fe (NO3)3·9H2The molar concentration of O- ethanol solution is 0.4 mol/L；
By step 2The forced air drying under the conditions of 60 DEG C of solution after stirring obtains black solid powder, this is consolidated
Body powder is transferred in crucible, and places it in 5 h of roast, the heating of the Muffle furnace under the conditions of 450 DEG C in Muffle furnace
Speed is 2 DEG C/min；
By step 2Black solid powder after middle roast is fully ground to obtain TOM-Co3O4/CoFe2O4, for use；
Three, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed, is transferred in brown shaking flask with aqueous solution containing Ciprofloxacin；
Four, single persulfate is added into the brown shaking flask into step 3, at 20 ~ 50 DEG C water-bath oscillating reactions 30 ~
120 min；
Five, magnetism TOM-Co is separated by externally-applied magnetic field3O4/CoFe2O4, the TOM-Co of recycling3O4/CoFe2O4With ethyl alcohol and
Deionized water is cleaned repeatedly and is dried in vacuo under the conditions of 60 DEG C, the TOM-Co recycled3O4/CoFe2O4。
Preferably, step 1Described in template KIT-6, Co (NO3)2·6H2The molar ratio of O is 1:1.
Preferably, step 1Described in Co (NO3)2·6H2The molar concentration of O solution is 0.8 mol/L.
Preferably, step 1Described in black solid and NaOH solution mass ratio be 1:100 ~ 200.
Preferably, step 2Described in TOM-Co3O4、Fe(NO3)3·9H2The molar ratio of O is 1:1.
Preferably, step 2Described in Fe (NO3)3·9H2The molar concentration of O- ethanol solution is 0.4 mol/L.
Preferably, TOM-Co described in step 33O4/CoFe2O4Dosage be every liter of aqueous solution containing Ciprofloxacin
10 ~ 200 mg of middle dispensing.
Preferably, concentration of aqueous solution containing Ciprofloxacin described in step 3 is 1 ~ 20 mg/L.
Preferably, single persulfate described in step 4 be Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and
At least one of single persulfuric acid calcium；The molar ratio of Ciprofloxacin is 66:1 in single persulfate and aqueous solution.
Meaning of the present invention is to solve catalyst (transition metal ions) recycling in homogeneous single persulfate activation systems to be stranded
It is difficult and the problem of easily cause secondary environmental pollution；It is small to solve currently used heterogeneous spinel-type specific surface area of catalyst,
The lower problem of catalytic capability；Solve heterogeneous TOM-Co3O4Activate catalyst reclaimer operation complexity in single persulfate system
Problem.The magnetic TOM-Co that the present invention uses3O4/CoFe2O4Have very big specific surface area and cellular structure abundant, it can
While adsorbed target organic matter, a large amount of oxygen-containing functional group in surface can further activate single persulfate, generate SO4 -It can
Accelerate the oxidative degradation of target contaminant.In TOM-Co3O4/CoFe2O4Use process in, metal ions M2+/M3+Valence state turn
The balance become between single persulfate decomposition ensure that catalyst performance continues efficient catalytic performance；TOM-Co3O4/
CoFe2O4It is easy to operate with good magnetic and reuse, reduce operating cost.
The present invention has the beneficial effect that:
1.TOM-Co3O4/CoFe2O4During being catalyzed single persulfate, digestion of metallic ion is very low, reduces ring
The secondary pollution in border.
2.TOM-Co3O4/CoFe2O4SO can be generated with efficient activation list persulfate4 -, easy to operate, energy saving,
Without carrying out ultraviolet irradiation, ultrasonic cavitation, heating etc. to system.
3.TOM-Co3O4/CoFe2O4With very big specific surface area and cellular structure abundant, can be easier and single mistake
Sulfate and organic pollutant contact, greatly improve catalytic efficiency.
4.TOM-Co3O4/CoFe2O4Surface oxygen-containing functional group rich in can be generated with efficient catalytic list persulfate
SO4 -Oxidative degradation organic matter, removal rate are more than 95 %.
5.TOM-Co3O4/CoFe2O4It can be recycled and reused by way of externally-applied magnetic field, reduce operating cost.
Detailed description of the invention
Fig. 1 is the relational graph of Ciprofloxacin Concentration percentage at any time under different working conditions.
Fig. 2 is reuse number to TOM-Co3O4/CoFe2O4Activate the influence diagram of single persulfate degradation Ciprofloxacin.
Fig. 3 is TOM-Co3O4/CoFe2O4By the effect picture through magnet absorption front and back, wherein left figure is to inhale without magnet
Attached effect picture, right figure are the effect picture adsorbed through magnet.
Specific embodiment
Technical solution of the present invention is not limited to specific implementation method exemplified below, further includes between each specific embodiment
Any combination.
Embodiment 1
One, TOM-Co is prepared3O4:
Co (NO is added to after template KIT-6 is fully ground3)2·6H2In O solution, 1 h is stirred at room temperature
Obtain solution A；
Step 1Described in template KIT-6, Co (NO3)2·6H2The molar ratio of O is 1:1；
Step 1Described in solution using ethyl alcohol as solvent；
Step 1Described in Co (NO3)2·6H2The molar concentration of O solution is 0.8 mol/L；
By step 1Acquired solution A forced air drying under the conditions of 60 DEG C obtains pink solid powder, this is consolidated
Body powder is transferred in crucible, and places it in 5 h of roast, the heating of the Muffle furnace under the conditions of 200 DEG C in Muffle furnace
Speed is 2 DEG C/min；
By step 1Brown solid powder after middle roast is added to Co (NO after being fully ground3)2·6H2O solution
In, 1 h is stirred at room temperature obtains solution B；
Step 1Described in solution using ethyl alcohol as solvent；
Step 1Described in Co (NO3)2·6H2The molar concentration of O solution is 0.8 mol/L；
By step 1Acquired solution B forced air drying under the conditions of 60 DEG C obtains black solid, this solid is shifted
To crucible, and place it in interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace；
Step 1Described in by black solid powder, 5 h of roast, the heating rate of Muffle furnace are under the conditions of 450 DEG C
2 ℃/min；
By step 1The black solid powder of middle roast is cooled to room temperature, and is added after being fully ground to filling 2
In the round-bottomed flask of mol/L NaOH solution, 12 h are stirred under 60 DEG C of water bath conditions, by 30 min of solution left standstill after stirring
Supernatant is removed, above step is in triplicate；
Step 1Described in black solid and 2 mol/L NaOH solutions mass ratio be 1:(100 ~ 200)；
By step 1Obtained in after material spends ultrapure water and ethanol washing to pH=7 respectively, 60 DEG C of vacuum
It is dried to obtain black solid, is stored for future use after this solid is fully ground.
Two, magnetism TOM-Co is prepared3O4/CoFe2O4:
By TOM-Co3O4It is added to Fe (NO3)3·9H2In O solution, 1 h is stirred at room temperature；
Step 1Described in TOM-Co3O4、Fe(NO3)3·9H2The molar ratio of O is 1:1；
Step 1Described in solution using ethyl alcohol as solvent；
Step 1Described in Fe (NO3)3·9H2The molar concentration of O solution is 0.4 mol/L；
By step 2The forced air drying under the conditions of 60 DEG C of solution after stirring obtains black solid powder, this is consolidated
Body powder is transferred in crucible, and places it in interior 5 h of roast under the conditions of 450 DEG C of Muffle furnace；
Step 2Described in by black solid powder under the conditions of 450 DEG C 5 h of roast, the heating rate of Muffle furnace
For 2 DEG C/min；
By step 2Black solid powder after middle roast is fully ground rear spare.
Three, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed, is transferred in brown shaking flask with aqueous solution containing Ciprofloxacin；
TOM-Co described in step 33O4/CoFe2O4Dosage be 10 ~ 50 mg/L;
Concentration of aqueous solution containing Ciprofloxacin described in step 3 is 1 ~ 5 mg/L；
It is 100 mL that mixed liquor volume in brown shaking flask is transferred to described in step 3.
Four, it adds single persulfate: single persulfate being added in brown shaking flask into step 3 and carries out Ciprofloxacin
Degradation reaction；
30 ~ 60 min of water-bath oscillating reactions under the conditions of holding reacting liquid temperature is 20 ~ 30 DEG C is, it can be achieved that cyclopropyl is husky in water
The efficient removal of star, and obtain containing TOM-Co3O4/CoFe2O4Mixed solution；
Single persulfate described in step 4 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid
One of calcium or in which several mixtures；
The molar ratio of Ciprofloxacin is (10 ~ 50) in single persulfate described in step 4 and aqueous solution: 1.
Five, magnetism TOM-Co is separated by externally-applied magnetic field3O4/CoFe2O4: magnetism TOM-Co is separated by externally-applied magnetic field3O4/
CoFe2O4, the TOM-Co of recycling3O4/CoFe2O4It is cleaned repeatedly with ethyl alcohol and deionized water and the vacuum under the conditions of 60 DEG C
It is dry, the TOM-Co recycled3O4/CoFe2O4；
TOM-Co described in step 53O4/CoFe2O4It is cleaned repeatedly with ethyl alcohol and deionized water, wash number is not
Less than 5 times.
Test Ciprofloxacin percentage changes with time situation, and change curve is shown in attached drawing 1.
Embodiment 2:
The concentration of target contaminant Ciprofloxacin is 5 ~ 10 mg/ to present embodiment in step 3 unlike the first embodiment
L, other steps and parameter are same as Example 1.
Embodiment 3:
The concentration of target contaminant Ciprofloxacin is 10 ~ 20 to present embodiment in step 3 unlike the first embodiment
Mg/L, other steps and parameter are same as Example 1.
Embodiment 4:
Present embodiment TOM-Co in step 3 unlike the first embodiment3O4/CoFe2O4Dosage be 50 ~ 100
Mg/L, other steps and parameter are same as Example 1.
Embodiment 5:
Present embodiment TOM-Co in step 3 unlike the first embodiment3O4/CoFe2O4Dosage be 100 ~ 200
Mg/L, other steps and parameter are same as Example 1.
Embodiment 6:
The molar ratio of single persulfate and target contaminant is present embodiment in step 4 unlike the first embodiment
(50 ~ 100): 1, other steps and parameter are same as Example 1.
Embodiment 7:
Single persulfate with the molar ratio containing Ciprofloxacin is present embodiment in step 4 unlike the first embodiment
(100 ~ 200): 1, other steps and parameter are same as Example 1.
Embodiment 8:
Temperature of reaction system is 30 ~ 50 DEG C to present embodiment in step 4 unlike the first embodiment, other steps and
Parameter is same as Example 1.
Embodiment 9:
The TOM-Co that present embodiment adds in step 3 unlike the first embodiment3O4/CoFe2O4To lead in step 5
Cross the TOM-Co of externally-applied magnetic field recycling3O4/CoFe2O4, other steps and parameter are same as Example 1.
Embodiment 10: multiple reuse of catalyst (TOM-Co3O4/CoFe2O4) PMS is activated to press Ciprofloxacin degradation experiment
Following methods carry out:
By magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed, is transferred in brown shaking flask with aqueous solution containing Ciprofloxacin；
TOM-Co described in step 33O4/CoFe2O4For the material recycled in step 5 by externally-applied magnetic field；
TOM-Co described in step 33O4/CoFe2O4Dosage be 100 mg/L；
Concentration of aqueous solution containing Ciprofloxacin described in step 3 is 5 mg/L；
It is 100 mL that mixed liquor volume in brown shaking flask is transferred to described in step 3.
Two, it adds single persulfate: single persulfate being added in brown shaking flask into step 3 and carries out Ciprofloxacin
Degradation reaction；
60 min of water-bath oscillating reactions is, it can be achieved that Ciprofloxacin in water under the conditions of to keep reacting liquid temperature be 25 ± 1 DEG C
Efficiently removal, and obtain containing TOM-Co3O4/CoFe2O4Mixed solution；
Single persulfate described in step 4 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid
One of calcium or in which several mixtures；
The molar ratio of Ciprofloxacin is 66:1 in single persulfate described in step 4 and aqueous solution.
Three, magnetism TOM-Co is separated by externally-applied magnetic field3O4/CoFe2O4: magnetism TOM-Co is separated by externally-applied magnetic field3O4/
CoFe2O4, the TOM-Co of recycling3O4/CoFe2O4It is cleaned repeatedly with ethyl alcohol and deionized water and the vacuum under the conditions of 60 DEG C
It is dry, the TOM-Co recycled3O4/CoFe2O4；
TOM-Co described in step 53O4/CoFe2O4It is cleaned repeatedly with ethyl alcohol and deionized water, wash number is not
Less than 5 times.
The different TOM-Co of reuse number3O4/CoFe2O4When testing with persulfate synergistic sorption Ciprofloxacin, cyclopropyl is husky
Star residual concentration and the relational graph of time are shown in attached drawing 2.
The TOM-Co after it can see repeatedly recycling in attached drawing 23O4/CoFe2O4Still maintain very high catalytic performance, the 5th
The TOM-Co of secondary recycling3O4/CoFe2O4Under conditions of coexisting with single persulfate, the removal rate of Ciprofloxacin is still high in 60 min
Up to 90 % or more.It can be seen that TOM-Co3O4/CoFe2O4Has good reuse.
Comparative example 1 individually adds TOM-Co3O4/CoFe2O4The adsorption experiment of Ciprofloxacin is carried out by the following method:
One, TOM-Co is prepared3O4: it is identical as 1 step 1 of embodiment；
Two, magnetism TOM-Co is prepared3O4/CoFe2O4: it is identical as 1 step 2 of embodiment；
Three, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed, is transferred in brown shaking flask with aqueous solution containing Ciprofloxacin,
Keeping reacting liquid temperature is 60 min of water-bath oscillating reactions under the conditions of 25 ± 1 DEG C, and is obtained containing TOM-Co3O4/CoFe2O4's
Mixed solution；
TOM-Co described in step 33O4/CoFe2O4Dosage be 100 mg/L；
Concentration of aqueous solution containing Ciprofloxacin described in step 3 is 5 mg/L；
It is 100 mL that mixed liquor volume in brown shaking flask is transferred to described in step 3.
Four, magnetism TOM-Co is separated by externally-applied magnetic field3O4/CoFe2O4: magnetism TOM-Co is separated by externally-applied magnetic field3O4/
CoFe2O4, the TOM-Co of recycling3O4/CoFe2O4After being cleaned repeatedly with ethyl alcohol and deionized water and in the condition under the conditions of 60 DEG C
Lower vacuum drying, the TOM-Co recycled3O4/CoFe2O4, then complete and individually add TOM-Co3O4/CoFe2O4To cyclopropyl sand
The adsorption experiment of star；
TOM-Co described in step 43O4/CoFe2O4It is cleaned repeatedly with ethyl alcohol and deionized water, wash number is no less than
5 times.
Test Ciprofloxacin percentage changes with time situation, and change curve is shown in attached drawing 1.
Comparative example 2 individually adds single persulfate and carries out by the following method to the oxidation experiment of Ciprofloxacin:
One, it prepares Ciprofloxacin aqueous solution: configuring certain density Ciprofloxacin aqueous solution and be transferred in brown shaking flask；
Concentration of aqueous solution containing Ciprofloxacin described in step 1 is 5 mg/L；
The mixed liquor volume described in step 1 that is transferred in brown shaking flask is 100 mL.
Two, it adds single persulfate: single persulfate being added and keeps reaction solution temperature in brown shaking flask into step 1
60 min of water-bath oscillating reactions is, it can be achieved that individually add oxidation of single persulfate to Ciprofloxacin under the conditions of degree is 25 ± 1 DEG C
Experiment；
Single persulfate described in step 4 is potassium hydrogen persulfate；
The molar ratio of Ciprofloxacin is 66:1 in single persulfate described in step 4 and aqueous solution.
By comparative example 1, comparative example 1 and comparative example 2, it can be found that: use TOM-Co of the present invention3O4/
CoFe2O4When cooperateing with both Ciprofloxacin ratios exclusive use in single persulfate adsorption aqueous solution, there is better adsorption effect.
The preferred embodiments of the invention are only listed above, and protection scope of the present invention is not restricted to this, this field
Made any change is each fallen in the scope of the present invention technical staff within the scope of the invention as claimed.
Claims (7)
1. a kind of method that antibacterials in single persulfate degradation water are activated based on the order mesoporous cobaltosic oxide of Fe2O3 doping,
It is characterized in that, specifically sequentially includes the following steps:
One, TOM-Co is prepared3O4:
Co (NO is added to after template KIT-6 is fully ground3)2·6H2In the ethanol solution of O, 1 is stirred at room temperature
H obtains solution A；
By step 1Acquired solution A forced air drying under the conditions of 60 DEG C obtains pink solid powder, by this solid powder
End is transferred in crucible, and is placed it in Muffle furnace and roasted 5 h, the heating rate of the Muffle furnace under the conditions of 200 DEG C
For 2 DEG C/min；
By step 1Brown solid powder after middle roasting is added to Co (NO after being fully ground3)2·6H2The ethyl alcohol of O is molten
In liquid, 1 h is stirred at room temperature and obtains solution B；
By step 1Acquired solution B forced air drying under the conditions of 60 DEG C obtains black solid, this solid is transferred to earthenware
It in crucible, and places it in Muffle furnace and roasts 5 h under the conditions of 450 DEG C, the heating rate of the Muffle furnace is 2 DEG C/min；
By step 1The black solid powder of middle roasting is cooled to room temperature, and is added after being fully ground to filling 2
In the round-bottomed flask of mol/L NaOH solution, 12 h are stirred under 60 DEG C of water bath conditions, by 30 min of solution left standstill after stirring
Supernatant is removed, above step is in triplicate；
By step 1Products obtained therefrom is cleaned to pH=7 with ultrapure water and ethyl alcohol repeatedly respectively, vacuum under the conditions of 60 DEG C
TOM-Co is fully ground to obtain after drying again3O4；
Two, magnetism TOM-Co is prepared3O4/CoFe2O4:
By TOM-Co3O4It is added to Fe (NO3)3·9H2In O- ethanol solution, 1 h is stirred at room temperature；
The TOM-Co3O4、Fe(NO3)3·9H2The molar ratio of O is 1:1；
Fe (the NO3)3·9H2The molar concentration of O- ethanol solution is 0.4 mol/L；
By step 2The forced air drying under the conditions of 60 DEG C of solution after stirring obtains black solid powder, by this solid powder
End is transferred in crucible, and is placed it in Muffle furnace and roasted 5 h, the heating rate of the Muffle furnace under the conditions of 450 DEG C
For 2 DEG C/min；
By step 2Black solid powder after middle roasting is fully ground to obtain TOM-Co3O4/CoFe2O4, for use；
Three, by magnetic TOM-Co3O4/CoFe2O4It is sufficiently mixed, is transferred in brown shaking flask with aqueous solution containing Ciprofloxacin；
Four, single persulfate is added into the brown shaking flask into step 3, the water-bath oscillating reactions 30 ~ 120 at 20 ~ 50 DEG C
min；
Five, magnetism TOM-Co is separated by externally-applied magnetic field3O4/CoFe2O4, the TOM-Co of recycling3O4/CoFe2O4With ethyl alcohol and go from
Sub- water is cleaned repeatedly and is dried in vacuo under the conditions of 60 DEG C, the TOM-Co recycled3O4/CoFe2O4。
2. the method for antibacterials in water of degrading as described in claim 1, which is characterized in that step 1Described in template
KIT-6、Co(NO3)2·6H2The molar ratio of O is 1:1.
3. the method for antibacterials in water of degrading as described in claim 1, which is characterized in that step 1Described in Co
(NO3)2·6H2The molar concentration of O solution is 0.8 mol/L.
4. the method for antibacterials in water of degrading as described in claim 1, which is characterized in that step 1Middle black solid with
The mass ratio of NaOH solution is 1:100 ~ 200.
5. the method for antibacterials in water of degrading as described in claim 1, which is characterized in that TOM- described in step 3
Co3O4/CoFe2O4Dosage be 10 ~ 200 mg of dispensing in every liter of aqueous solution containing Ciprofloxacin.
6. the method for antibacterials in water of degrading as described in claim 1, which is characterized in that husky containing cyclopropyl described in step 3
Star concentration of aqueous solution is 1 ~ 20 mg/L.
7. the method for antibacterials in water of degrading as described in claim 1, which is characterized in that single persulfuric acid described in step 4
Salt is at least one of Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium；Single persulfate with
The molar ratio of Ciprofloxacin is 66:1 in aqueous solution.
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| CN105399197A (en) * | 2015-12-15 | 2016-03-16 | 浙江工业大学 | Method for processing dye waste water based on activation of peroxymonosufate by three-dimensional ordered mesoporous CoFe2O4 |
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| CN105399197A (en) * | 2015-12-15 | 2016-03-16 | 浙江工业大学 | Method for processing dye waste water based on activation of peroxymonosufate by three-dimensional ordered mesoporous CoFe2O4 |
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