CN106732604A - The method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate - Google Patents
The method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate Download PDFInfo
- Publication number
- CN106732604A CN106732604A CN201611144333.7A CN201611144333A CN106732604A CN 106732604 A CN106732604 A CN 106732604A CN 201611144333 A CN201611144333 A CN 201611144333A CN 106732604 A CN106732604 A CN 106732604A
- Authority
- CN
- China
- Prior art keywords
- mgo
- antibacterials
- solid powder
- under
- conditions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J32/00—
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Method the invention discloses antibacterials in water removal are gone using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate, operating procedure is as follows：Prepare cobaltosic oxide/order mesoporous magnesium oxide composite material；Prepare solution of the finite concentration containing antibacterials；Cobaltosic oxide/order mesoporous magnesia is added, mixes certain hour to reach adsorption equilibrium；Add Potassium peroxysulfate；By being centrifuged or being separated by filtration cobaltosic oxide/order mesoporous magnesium oxide composite material, you can complete a kind of method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate.The efficient process of antibacterials in water can be realized using the method for the present invention, clearance is more than 95%；Cobalt ions dissolution concentration is less than nano-cobaltic-cobaltous oxide during use, reduces environmental pollution；Cobaltosic oxide/order mesoporous magnesium oxide composite material can reduce operating cost by being centrifuged or being separated by filtration and recycle.
Description
Technical field
The invention belongs to water treatment field, and in particular to a kind of method for going antibacterials in water removal, more particularly to a kind of utilization
The method that order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate goes antibacterials in water removal.
Background technology
Medicine and personal-care supplies（Pharmaceuticals and Personal Care Products, PPCPs）Into
It is a kind of emerging environmental contaminants, is detected in the surrounding mediums such as underground water, surface water, soil, and is proved to right
Environment and human health cause certain harm.Enrofloxacin（Enrofloxacin, ENR）Belong to carbostyril family antibacterial drugs,
It is widely used in the treatment of the mankind and Animal diseases.After the Enrofloxacin of residual enters human body, toxic and side effect can be produced to human body, and
Greatly enhance the drug resistance of human body pathogen.On the other hand, after animal has taken in a large amount of Enrofloxacins, excreted with fecaluria,
Enter into natural environment, the ecosystem is constituted potentially hazardous.Enrofloxacin shares medicine as a kind of people and animals, and medicine is residual
Stay bigger to human health damage by food chain.There is research to point out, Enrofloxacin is more difficult to be degraded by microorganisms, and can not be normal
Rule water treatment technology is effectively removed.Therefore, need badly and find the pollution problem that effective treating method solves Enrofloxacin in environment.
In recent years, based on potentiometric titrations SO4 -High-level oxidation technology receive the extensive concern of researcher.Its
The middle single persulfate of cobalt ions activation（Peroxymonosufate, PMS）System produces the SO of Strong oxdiative activity4 -In room temperature
It is lower efficiently to carry out, without external energy（Ultrasound, thermal source and light source）, it is considered to be activation method the most efficient.Grind
Study carefully discovery, heterogeneous single persulfate activation system can efficiently solve that activator reclaims difficult and to easily cause environment secondary
The problems such as pollution.Anipsitakis etc. is attempted commercial Co first3O4The single persulfate of heterogeneous activation is applied to, and in degraded
Gratifying result is achieved during 2,4- chlorophenols.On the basis of this achievement, Chen etc. has found nano Co3O4Urging
The cobalt ions dissolution of good application prospect and low concentration is shown during changing single persulfate.During application
Find simultaneously, nano Co3O4Specific surface area it is relatively low, and reunion serious in the solution reduce further it with single persulfuric acid
The touch opportunity of salt, hence it is evident that inhibit activation effect.
The content of the invention
It is an object of the invention to solve nano Co3O4The relatively low problem of efficiency, exploitation one during the single persulfate of activation
Plant the method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate.
The technical solution adopted for the present invention to solve the technical problems is：
The method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate, it is described
Method is carried out according to the following steps：
（1）Prepare ordered mesopore carbon CMK-3
1. template mesoporous molecular sieve SBA-15 is sufficiently mixed with the aqueous sulfuric acid containing sucrose, at 100 DEG C dry 5
H, under the conditions of 160 DEG C dry 5 h obtain solid powder A；
2. by step 1. in the solid powder A that is dried to obtain be fully ground after be sufficiently mixed with aqueous sucrose solution, in 100 DEG C of bars
Under part dry 5 h, under the conditions of 160 DEG C dry 5 h obtain solid powder B；
3. by step, 2. dried solid powder B is transferred in crucible, and is placed into tube furnace in 900 DEG C of vacuum bars
The h of roast 5 under part, the programming rate of the Muffle furnace is 2 DEG C/min；
4. the solid powder B of step 3. middle roast is cooled to room temperature, through being fully ground after input fill 1 mol/L NaOH
In the reaction vessel of the aqueous solution, in stirring 12 h under 70 DEG C of water bath conditions, the min of solution left standstill 30 after stirring is fallen into supernatant
Liquid, above step is in triplicate；
5. by step 4. in the material that obtains spend ultra-pure water and ethanol and clean repeatedly to pH=7, the vacuum under the conditions of 120 DEG C
CMK-3 solid powders are dried to obtain, are stored for future use after this solid powder is fully ground；
（2）Prepare OM-MgO
1. by step（1）In the CMK-3 solid powders that obtain be added to Mg (NO3)2·6H2In O solution, stir at ambient temperature
Mix 2 h, after 3 h are calcined under 300 DEG C of vacuum conditions in tube furnace, the programming rate of the tube furnace is 2 DEG C/min；
2. by step 1. in method in triplicate；
3. the solid powder after step 2. middle vacuum baking is calcined 3 h in Muffle furnace under the conditions of 800 DEG C, CMK-3 is removed
Template, the programming rate of the Muffle furnace is 2 DEG C/min；
4. the sample after step 3. middle roasting is cooled to room temperature and obtains OM-MgO solid powders, this solid powder is fully ground
Stored for future use after mill；
（3）Prepare Co3O4/OM-MgO
1. OM-MgO is added to Co (NO3)3·6H2In O- ethanol solutions, 2 h are stirred at ambient temperature；
2. the solution after 1. step is stirred obtains solid powder in forced air drying at 60 DEG C, and this solid powder is transferred into earthenware
In crucible, and place it in Muffle furnace the h of roast 3 under the conditions of 500 DEG C, the programming rate of the Muffle furnace for 2 DEG C/
min；
3. by the Co after step 2. middle roast3O4/ OM-MgO solid powders are fully ground rear standby；
（4）By Co3O4/ OM-MgO is sufficiently mixed with the aqueous solution containing Enrofloxacin, is transferred in brown shaking flask；
（5）Add single persulfate：Single persulfate is added to step（4）In brown shaking flask in carry out the drop of Enrofloxacin
Solution reaction；It is the min of water-bath concussion reaction 30 ~ 120 under conditions of 20 ~ 50 DEG C to keep reacting liquid temperature, is capable of achieving grace promise in water
The efficient removal of Sha Xing, and obtain containing Co3O4The mixed solution of/OM-MgO；
（6）Co is reclaimed using centrifugation or filter type3O4/ OM-MgO, the Co of recovery3O4/ OM-MgO ethanol and deionized water are anti-
Multiple cleaning at least 5 times, and in 60 DEG C of vacuum drying, the Co being recycled3O4/OM-MgO。
Preferably, step（1）The quality of template SBA-15, sucrose and aqueous sulfuric acid described in 1. is 1：1.25：
5.14 g；The mass concentration of the aqueous sulfuric acid is 2.72%.
Preferably, step（1）The quality that the mass concentration of the aqueous sucrose solution described in 2. is is 19.56%, described solid
Body powders A is 2.39 with the mass ratio of aqueous sucrose solution：1.25；
Preferably, step（1）4. solid powder B and the mass ratio of the NaOH aqueous solution described in are 1：100~200.
Preferably, step（2）The inventory of the CMK-3 solid powders described in 1. is 50g/L Mg (NO3)2·6H2O
Solution, described Mg (NO3)2·6H2The molar concentration of O is 0.25 mol/L.
Preferably, step（3）1. OM-MgO, Co (NO described in3)3·6H2The mol ratio of O is 5:1, described Co
(NO3)3·6H2The molar concentration of O- ethanol solutions is 0.5 mol/L.
Preferably, step（4）Described in Co3O4The dosage of/OM-MgO is 10 ~ 500 mg/L water containing Enrofloxacin
Solution；
Preferably, step（4）Described in concentration of aqueous solution containing Enrofloxacin be 1 ~ 20 mg/L；
Preferably, step（5）Described in single persulfate be selected from Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and
At least one in single persulfuric acid calcium.
Preferably, step（5）Described in single persulfate and the aqueous solution in the mol ratio of Enrofloxacin be 10 ~ 200：
1。
Supported activator can not only improve nano Co3O4Dispersiveness in the solution, and cobalt can be efficiently reduced
The dissolution of ion.What is more important, metal oxide carrier（Such as TiO2And Al2O3Deng）Surface C o-OH is advantageously formed to be combined
Thing, so as to accelerate the decomposition of single persulfate.MgO is a kind of white solid, is generally present in nature in periclase form, is
Widely used fire retardant, the annual production of China MgO is up to 12,000,000 tons.In recent years, it is order mesoporous（Ordered
Mesoporous, OM）Metal oxide is favored in catalytic field.Ordered mesoporous metal oxide possesses high ratio table
Area and abundant three-dimensional open-framework, can form lattice defect and Lacking oxygen, so as to produce substantial amounts of in catalyst surface
Active oxygen.If the MgO of ordered mesopore structure can be prepared, as nano Co3O4Carrier, then MgO surfaces enrich
Basic site can be obviously improved nano Co3O4To the activity function of single persulfate.
The Co that the present invention is developed3O4/ OM-MgO composite nano materials possess great specific surface area and abundant duct knot
Structure, the abundant basic site in OM-MgO surfaces can form substantial amounts of surface C o-OH compounds, so as to accelerate single persulfate
Decompose.Additionally, the composite nanometer particle has adhered to nano Co3O4Advantage, metal ion Co2+/Co3+Valence transition and single mistake
Balance between sulphate decomposition ensure that catalyst is played and continue efficient catalytic performance.
Beneficial effects of the present invention are as follows：
Co of the invention3O4/ OM-MgO composite nano materials possess extremely strong activity function to single persulfate；
Co of the invention3O4/ OM-MgO composite nano materials use rear recyclable recycling, reduce operating cost；
The present invention is simple to operate, it is easy to accomplish；
The method applied in the present invention can further reduce cobalt ions dissolution concentration, and environmental pollution is minimum；
The method applied in the present invention can effectively remove Enrofloxacin in water removal, and clearance is more than 95%；
The method applied in the present invention can expand and be applied to other hardly degraded organic substances in water, and such as organic dyestuff, agricultural chemicals go
Remove.
Brief description of the drawings
Fig. 1 is Enrofloxacin removal versus time curve figure under the conditions of differential responses.
Fig. 2 is Co3O4/ OM-MgO is by five change curves using catalytic performance.
Specific embodiment
Below by specific embodiment, and with reference to accompanying drawing, technical scheme is described in further detail.
Technical solution of the present invention is not limited to specific implementation method exemplified below, also including appointing between each specific embodiment
Meaning combination.
Specific embodiment one：It is a kind of in present embodiment to activate list using order mesoporous MgO-Supported cobaltosic oxide
The method that potassium peroxydisulfate goes antibacterials in water removal, is carried out according to the following steps：
（1）Prepare CMK-3
1. template SBA-15 is sufficiently mixed with the aqueous sulfuric acid containing sucrose, 5 h is dried under the conditions of 100 DEG C, afterwards
5 h are dried under the conditions of 160 DEG C and obtains solid powder；
Step 1. described in template SBA-15 mass be 1 g；
Step 1. described in sucrose quality be 1.25 g；
Step 1. described in sulfuric acid quality be 0.14 g；
Step 1. described in water quality be 5 g；
2. by step 1. in the solid powder that is dried to obtain be fully ground after be sufficiently mixed with aqueous sucrose solution, in 100 DEG C of bars
Under part dry 5 h, under the conditions of 160 DEG C dry 5 h obtain solid powder；
Step 2. described in sucrose quality be 0.8 g；
Step 2. described in sulfuric acid quality be 0.09 g；
Step 2. described in water volume be 5 g；
3. by step, 2. dried solid powder is transferred in crucible, and is placed into tube furnace in 900 DEG C of vacuum bars
The h of roast 5 under part；
Step 3. described in solid powder is placed in the h of roast 5 under 900 DEG C of vacuum conditions, the programming rate of Muffle furnace is 2
℃/min；
4. the solid powder of step 3. middle roast is cooled to room temperature, through being fully ground after add to filling 1 mol/L
In the round-bottomed flask of NaOH solution, in 12 h are stirred under 70 DEG C of water bath conditions, the min of solution left standstill 30 after stirring is fallen
Clear liquid, above step is in triplicate；
Step 4. described in 1 mol/L NaOH solutions in, the volume ratio of solvent deionized water and ethanol is 1:1；
Step 4. described in solid and 2 mol/L NaOH solutions mass ratio be 1:(100~200)；
5. by step 4. in the material that obtains spend ultra-pure water and ethanol and clean repeatedly to pH=7, the vacuum under the conditions of 120 DEG C
CMK-3 solid powders are dried to obtain, are stored for future use after this solid powder is fully ground.
（2）Prepare OM-MgO
1. the CMK-3 solid powders that will be obtained in step one are added to Mg (NO3)2·6H2In O solution, stir at ambient temperature
Mix 2 h, after being calcined 3 h under 300 DEG C of vacuum conditions in tube furnace；
Step 1. described in CMK-3 solid powders quality be 0.5 g；
Step 1. described in Mg (NO3)2·6H2The molar concentration of O is 0.25 mol/L；
Step 1. described in Mg (NO3)2·6H2The volume of O solution is 10 mL；
Step 1. described in 300 DEG C under the conditions of be calcined 3 h, the programming rate of tube furnace is 2 DEG C/min；
2. by step 1. in method in triplicate；
3. the solid powder after step 2. middle vacuum baking is calcined 3 h in Muffle furnace under the conditions of 800 DEG C, CMK-3 is removed
Template；
Step 3. described in Muffle furnace programming rate be 2 DEG C/min；
4. the sample after step 3. middle roasting is cooled to room temperature and obtains OM-MgO solid powders, this solid powder is fully ground
Stored for future use after mill.
（3）Prepare Co3O4/OM-MgO
1. the OM-MgO of certain mass is added to Co (NO3)3·6H2In O solution, 2 h are stirred at ambient temperature；
Step 1. described in OM-MgO, Co (NO3)3·6H2The mol ratio of O is 5:1；
Step 1. described in solution with ethanol as solvent；
Step 1. described in Co (NO3)3·6H2The molar concentration of O solution is 0.5 mol/L；
2. the forced air drying under the conditions of 60 DEG C of solution after 1. step is stirred obtains solid powder, by the transfer of this solid powder
To crucible, and place it in the interior h of roast 3 under the conditions of 500 DEG C of Muffle furnace；
Step 2. described in by black solid powder under the conditions of 500 DEG C the h of roast 3, the programming rate of Muffle furnace for 2 DEG C/
min；
3. by the Co after step 2. middle roast3O4/ OM-MgO solid powders are fully ground rear standby.
（4）By Co3O4/ OM-MgO is sufficiently mixed with the aqueous solution containing Enrofloxacin, is transferred in brown shaking flask；
Step（4）Described in Co3O4The dosage of/OM-MgO is 10 ~ 500 mg/L；
Step（4）Described in concentration of aqueous solution containing Enrofloxacin be 1 ~ 20 mg/L；
Step（4）Described in the mixed liquor volume being transferred in brown shaking flask be 100 ~ 200 mL.
（5）Add single persulfate：Enrofloxacin is carried out in the brown shaking flask for adding into step 4 by single persulfate
Degradation reaction；It is the min of water-bath concussion reaction 30 ~ 120 under conditions of 20 ~ 50 DEG C to keep reacting liquid temperature, is capable of achieving in water
The efficient removal of Enrofloxacin, and obtain containing Co3O4The mixed solution of/OM-MgO；
Step（5）Described in single persulfate be Potassium peroxysulfate, in single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium
One kind or wherein several mixtures；
Step（5）Described in single persulfate and the aqueous solution in the mol ratio of Enrofloxacin be (10 ~ 200):1.
（6）Co is reclaimed using centrifugation or filter type3O4/OM-MgO：The Co of recovery3O4/ OM-MgO ethanol and deionization
Water is cleaned and in 60 DEG C of vacuum drying, the Co being recycled repeatedly3O4/OM-MgO；
Step（6）Described in Co3O4/ OM-MgO ethanol and deionized water are cleaned repeatedly, and wash number is no less than 5 times.
Specific embodiment two：Present embodiment and step unlike specific embodiment one（4）Middle target contaminant
The concentration of Enrofloxacin is 5 ~ 10 mg/L, and other steps and parameter are identical with specific embodiment one.
Specific embodiment three：Present embodiment and step unlike specific embodiment one to two（4）Middle target is dirty
The concentration for contaminating thing Enrofloxacin is 10 ~ 20 mg/L, and other steps and parameter are identical with one of specific embodiment one to two.
Specific embodiment four：Step unlike one of present embodiment and specific embodiment one to three（4）In
Co3O4The dosage of/OM-MgO is 50 ~ 200 mg/L.Other steps and parameter are identical with one of specific embodiment one to three.
Specific embodiment five：Step unlike one of present embodiment and specific embodiment one to four（4）In
Co3O4The dosage of/OM-MgO is 200 ~ 500 mg/L.Other steps and parameter are identical with one of specific embodiment one to four.
Specific embodiment six：Present embodiment and step unlike specific embodiment one to five（5）Middle single over cure
Hydrochlorate is (50 ~ 100) with the mol ratio of target contaminant:1.One of other steps and parameter and specific embodiment one to five phase
Together.
Specific embodiment seven：Present embodiment and step unlike specific embodiment one to six（5）Middle single over cure
Hydrochlorate is (100 ~ 200) with the mol ratio of Enrofloxacin:1.One of other steps and parameter and specific embodiment one to six phase
Together.
Specific embodiment eight：Step unlike one of present embodiment and specific embodiment one to seven（5）In it is anti-
It is 30 ~ 50 DEG C to answer system temperature.Other steps and parameter are identical with one of specific embodiment one to seven.
Specific embodiment nine：Step unlike one of present embodiment and specific embodiment one to eight（4）Middle throwing
Plus Co3O4/ OM-MgO is step（6）In by way of being centrifuged or filtering the Co that reclaims3O4/OM-MgO.Other steps and ginseng
Number is identical with one of specific embodiment one to eight.
In order to verify beneficial effects of the present invention, following experiment has been carried out：
Comparative example 1：Individually add Co3O4/ OM-MgO is carried out by the following method to the adsorption experiment of Enrofloxacin：
（1）Prepare CMK-3
1. template SBA-15 is sufficiently mixed with the aqueous sulfuric acid containing sucrose, 5 h is dried under the conditions of 100 DEG C, afterwards
5 h are dried under the conditions of 160 DEG C and obtains solid powder；
Step 1. described in template SBA-15 mass be 1 g；
Step 1. described in sucrose quality be 1.25 g；
Step 1. described in sulfuric acid quality be 0.14 g；
Step 1. described in water quality be 5 g；
2. by step 1. in the solid powder that is dried to obtain be fully ground after be sufficiently mixed with aqueous sucrose solution, in 100 DEG C of bars
Under part dry 5 h, under the conditions of 160 DEG C dry 5 h obtain solid powder；
Step 2. described in sucrose quality be 0.8 g；
Step 2. described in sulfuric acid quality be 0.09 g；
Step 2. described in water volume be 5 g；
3. by step, 2. dried solid powder is transferred in crucible, and is placed into tube furnace in 900 DEG C of vacuum bars
The h of roast 5 under part；
Step 3. described in solid powder is placed in the h of roast 5 under 900 DEG C of vacuum conditions, the programming rate of Muffle furnace is 2
℃/min；
4. the solid powder of step 3. middle roast is cooled to room temperature, through being fully ground after add to filling 1 mol/L
In the round-bottomed flask of NaOH solution, in 12 h are stirred under 70 DEG C of water bath conditions, the min of solution left standstill 30 after stirring is fallen
Clear liquid, above step is in triplicate；
Step 4. described in 1 mol/L NaOH solutions in, the volume ratio of solvent deionized water and ethanol is 1:1；
Step 4. described in solid and 2 mol/L NaOH solutions mass ratio be 1:100；
5. by step 4. in the material that obtains spend ultra-pure water and ethanol and clean repeatedly to pH=7, the vacuum under the conditions of 120 DEG C
CMK-3 solid powders are dried to obtain, are stored for future use after this solid powder is fully ground.
（2）Prepare OM-MgO
1. the CMK-3 solid powders that will be obtained in step one are added to Mg (NO3)2·6H2In O solution, stir at ambient temperature
Mix 2 h, after being calcined 3 h under 300 DEG C of vacuum conditions in tube furnace；
Step 1. described in CMK-3 solid powders quality be 0.5 g；
Step 1. described in Mg (NO3)2·6H2The molar concentration of O is 0.25 mol/L；
Step 1. described in Mg (NO3)2·6H2The volume of O solution is 10 mL；
Step 1. described in 300 DEG C under the conditions of be calcined 3 h, the programming rate of tube furnace is 2 DEG C/min；
2. by step 1. in method in triplicate；
3. the solid powder after step 2. middle vacuum baking is calcined 3 h in Muffle furnace under the conditions of 800 DEG C, CMK-3 is removed
Template；
Step 3. described in Muffle furnace programming rate be 2 DEG C/min；
4. the sample after step 3. middle roasting is cooled to room temperature and obtains OM-MgO solid powders, this solid powder is fully ground
Stored for future use after mill.
（3）Prepare Co3O4/OM-MgO
1. the OM-MgO of certain mass is added to Co (NO3)3·6H2In O solution, 2 h are stirred at ambient temperature；
Step 1. described in OM-MgO, Co (NO3)3·6H2The mol ratio of O is 5:1；
Step 1. described in solution with ethanol as solvent；
Step 1. described in Co (NO3)3·6H2The molar concentration of O solution is 0.5 mol/L；
2. the forced air drying under the conditions of 60 DEG C of solution after 1. step is stirred obtains solid powder, by the transfer of this solid powder
To crucible, and place it in the interior h of roast 3 under the conditions of 500 DEG C of Muffle furnace；
Step 2. described in by black solid powder under the conditions of 500 DEG C the h of roast 3, the programming rate of Muffle furnace for 2 DEG C/
min；
3. by the Co after step 2. middle roast3O4/ OM-MgO solid powders are fully ground rear standby.
（3）Prepare Co3O4/OM-MgO
1. the OM-MgO of certain mass is added to Co (NO3)3·6H2In O solution, 2 h are stirred at ambient temperature；
Step 1. described in OM-MgO, Co (NO3)3·6H2The mol ratio of O is 5:1；
Step 1. described in solution with ethanol as solvent；
Step 1. described in Co (NO3)3·6H2The molar concentration of O solution is 0.5 mol/L；
2. the forced air drying under the conditions of 60 DEG C of solution after 1. step is stirred obtains solid powder, by the transfer of this solid powder
To crucible, and place it in the interior h of roast 3 under the conditions of 500 DEG C of Muffle furnace；
Step 2. described in by black solid powder under the conditions of 500 DEG C the h of roast 3, the programming rate of Muffle furnace for 2 DEG C/
min；
3. by the Co after step 2. middle roast3O4/ OM-MgO solid powders are fully ground rear standby.
（4）By Co3O4/ OM-MgO is sufficiently mixed with the aqueous solution containing Enrofloxacin, is transferred in brown shaking flask；
Step（4）Described in Co3O4The dosage of/OM-MgO is 200 mg/L；
Step（4）Described in concentration of aqueous solution containing Enrofloxacin be 10 mg/L；
Step（4）Described in the mixed liquor volume being transferred in brown shaking flask be 100 mL.
Comparative example 2：Individually add single persulfate is carried out by the following method to the oxidation experiment of Enrofloxacin：
（1）Prepare the Enrofloxacin aqueous solution：Configure the certain density Enrofloxacin aqueous solution and be transferred in brown shaking flask；
Step（1）Described in concentration of aqueous solution containing Enrofloxacin be 5 mg/L；
Step（1）Described in the mixed liquor volume in brown shaking flask that is transferred to be 100 mL.
（2）Add single persulfate：Single persulfate is added to step（1）In brown shaking flask in keep reaction liquid temperature
It is the min of water-bath concussion reaction 60 under the conditions of 25 ± 1 DEG C to spend, and is capable of achieving individually to add oxidation of single persulfate to Enrofloxacin
Experiment；
Step（2）Described in single persulfate be potassium hydrogen persulfate；
Step（2）Described in single persulfate and the aqueous solution in the mol ratio of Enrofloxacin be 100:1.
Embodiment 2：Multiple reuse is to Co3O4The influence experiment of/OM-MgO catalysis activities is carried out by the following method：
（1）Prepare CMK-3
1. template SBA-15 is sufficiently mixed with the aqueous sulfuric acid containing sucrose, 5 h is dried under the conditions of 100 DEG C, afterwards
5 h are dried under the conditions of 160 DEG C and obtains solid powder；
Step 1. described in template SBA-15 mass be 1 g；
Step 1. described in sucrose quality be 1.25 g；
Step 1. described in sulfuric acid quality be 0.14 g；
Step 1. described in water quality be 5 g；
2. by step 1. in the solid powder that is dried to obtain be fully ground after be sufficiently mixed with aqueous sucrose solution, in 100 DEG C of bars
Under part dry 5 h, under the conditions of 160 DEG C dry 5 h obtain solid powder；
Step 2. described in sucrose quality be 0.8 g；
Step 2. described in sulfuric acid quality be 0.09 g；
Step 2. described in water volume be 5 g；
3. by step, 2. dried solid powder is transferred in crucible, and is placed into tube furnace in 900 DEG C of vacuum bars
The h of roast 5 under part；
Step 3. described in solid powder is placed in the h of roast 5 under 900 DEG C of vacuum conditions, the programming rate of Muffle furnace is 2
℃/min；
4. the solid powder of step 3. middle roast is cooled to room temperature, through being fully ground after add to filling 1 mol/L
In the round-bottomed flask of NaOH solution, in 12 h are stirred under 70 DEG C of water bath conditions, the min of solution left standstill 30 after stirring is fallen
Clear liquid, above step is in triplicate；
Step 4. described in 1 mol/L NaOH solutions in, the volume ratio of solvent deionized water and ethanol is 1:1；
Step 4. described in solid and 2 mol/L NaOH solutions mass ratio be 1:100；
5. by step 4. in the material that obtains spend ultra-pure water and ethanol and clean repeatedly to pH=7, the vacuum under the conditions of 120 DEG C
CMK-3 solid powders are dried to obtain, are stored for future use after this solid powder is fully ground.
（2）Prepare OM-MgO
1. the CMK-3 solid powders that will be obtained in step one are added to Mg (NO3)2·6H2In O solution, stir at ambient temperature
Mix 2 h, after being calcined 3 h under 300 DEG C of vacuum conditions in tube furnace；
Step 1. described in CMK-3 solid powders quality be 0.5 g；
Step 1. described in Mg (NO3)2·6H2The molar concentration of O is 0.25 mol/L；
Step 1. described in Mg (NO3)2·6H2The volume of O solution is 10 mL；
Step 1. described in 300 DEG C under the conditions of be calcined 3 h, the programming rate of tube furnace is 2 DEG C/min；
2. by step 1. in method in triplicate；
3. the solid powder after step 2. middle vacuum baking is calcined 3 h in Muffle furnace under the conditions of 800 DEG C, CMK-3 is removed
Template；
Step 3. described in Muffle furnace programming rate be 2 DEG C/min；
4. the sample after step 3. middle roasting is cooled to room temperature and obtains OM-MgO solid powders, this solid powder is fully ground
Stored for future use after mill.
（3）Prepare Co3O4/OM-MgO
1. the OM-MgO of certain mass is added to Co (NO3)3·6H2In O solution, 2 h are stirred at ambient temperature；
Step 1. described in OM-MgO, Co (NO3)3·6H2The mol ratio of O is 5:1；
Step 1. described in solution with ethanol as solvent；
Step 1. described in Co (NO3)3·6H2The molar concentration of O solution is 0.5 mol/L；
2. the forced air drying under the conditions of 60 DEG C of solution after 1. step is stirred obtains solid powder, by the transfer of this solid powder
To crucible, and place it in the interior h of roast 3 under the conditions of 500 DEG C of Muffle furnace；
Step 2. described in by black solid powder under the conditions of 500 DEG C the h of roast 3, the programming rate of Muffle furnace for 2 DEG C/
min；
3. by the Co after step 2. middle roast3O4/ OM-MgO solid powders are fully ground rear standby.
（4）By Co3O4/ OM-MgO is sufficiently mixed with the aqueous solution containing Enrofloxacin, is transferred in brown shaking flask；
Step（4）Described in Co3O4The dosage of/OM-MgO is 200 mg/L；
Step（4）Described in concentration of aqueous solution containing Enrofloxacin be 10 mg/L；
Step（4）Described in the mixed liquor volume being transferred in brown shaking flask be 100 mL.
（5）Add single persulfate：Enrofloxacin is carried out in the brown shaking flask for adding into step 4 by single persulfate
Degradation reaction；It is the min of water-bath concussion reaction 60 under conditions of 25 DEG C to keep reacting liquid temperature, is capable of achieving Enrofloxacin in water
Efficient removal, and obtain containing Co3O4The mixed solution of/OM-MgO；
Step（5）Described in single persulfate be Potassium peroxysulfate, in single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium
One kind or wherein several mixtures；
Step（5）Described in single persulfate and the aqueous solution in the mol ratio of Enrofloxacin be 100:1.
（6）Co is reclaimed using centrifugation or filter type3O4/OM-MgO：The Co of recovery3O4/ OM-MgO ethanol and deionization
Water is cleaned and in 60 DEG C of vacuum drying, the Co being recycled repeatedly3O4/OM-MgO.Repeat step（4）, then recovery is completed
Co3O4The catalytic performance experiment of/OM-MgO.
Step（6）Described in Co3O4/ OM-MgO ethanol and deionized water are cleaned repeatedly, and wash number is no less than 5 times.
Enrofloxacin concentration changes with time situation as shown in figure 1, can from figure in embodiment 1, comparative example 1 ~ 2
Arrive, Co3O4Under conditions of/OM-MgO and single persulfate coexist, Enrofloxacin concentration occurs in that obvious reduction over time,
Clearance has exceeded 95%；And individually add Co3O4During/OM-MgO, Enrofloxacin has only been removed less than 2 % in 60 min；It is single
When solely adding single persulfate, Enrofloxacin only has 20 % and is oxidized in 60 min.Reuse number of times is to Co in embodiment 23O4/OM-
The influence of the single persulfate degraded Enrofloxacin of MgO collaborations is as shown in Fig. 2 Co after repeatedly reclaiming3O4/ OM-MgO is remained in that very
High catalytic performance, the 5th Co of recovery3O4Under conditions of/OM-MgO and single persulfate coexist, Enrofloxacin in 60 min
Clearance is still up to 90 more than %, it can be seen that, Co3O4/ OM-MgO possesses good reuse.
Claims (10)
1. the method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate, its
It is characterised by, carries out according to the following steps：
（1）Prepare CMK-3
1. template mesoporous molecular sieve SBA-15 is sufficiently mixed with the aqueous sulfuric acid containing sucrose, at 100 DEG C dry 5
H, under the conditions of 160 DEG C dry 5 h obtain solid powder A；
2. by step 1. in the solid powder A that is dried to obtain be fully ground after be sufficiently mixed with aqueous sucrose solution, in 100 DEG C of bars
Under part dry 5 h, under the conditions of 160 DEG C dry 5 h obtain solid powder B；
3. by step, 2. dried solid powder B is transferred in crucible, and is placed into tube furnace in 900 DEG C of vacuum bars
The h of roast 5 under part, the programming rate of the Muffle furnace is 2 DEG C/min；
4. the solid powder B of step 3. middle roast is cooled to room temperature, through being fully ground after add into filling 1 mol/L
In the reaction vessel of the NaOH aqueous solution, in 12 h are stirred under 70 DEG C of water bath conditions, the min of solution left standstill 30 after stirring is fallen
Supernatant, above step is in triplicate；
5. by step 4. in the material that obtains spend ultra-pure water and ethanol and clean repeatedly to pH=7, the vacuum under the conditions of 120 DEG C
CMK-3 solid powders are dried to obtain, are stored for future use after this solid powder is fully ground；
（2）Prepare OM-MgO
1. by step（1）In the CMK-3 solid powders that obtain be added to Mg (NO3)2·6H2In O solution, stir at ambient temperature
Mix 2 h, after 3 h are calcined under 300 DEG C of vacuum conditions in tube furnace, the programming rate of the tube furnace is 2 DEG C/min；
2. by step 1. in method in triplicate；
3. the solid powder after step 2. middle vacuum baking is calcined 3 h in Muffle furnace under the conditions of 800 DEG C, CMK-3 is removed
Template, the programming rate of the Muffle furnace is 2 DEG C/min；
4. the sample after step 3. middle roasting is cooled to room temperature and obtains OM-MgO solid powders, this solid powder is fully ground
Stored for future use after mill；
（3）Prepare Co3O4/OM-MgO
1. OM-MgO is added to Co (NO3)3·6H2In O- ethanol solutions, 2 h are stirred at ambient temperature；
2. the solution after 1. step is stirred obtains solid powder in forced air drying at 60 DEG C, and this solid powder is transferred into earthenware
In crucible, and place it in Muffle furnace the h of roast 3 under the conditions of 500 DEG C, the programming rate of the Muffle furnace for 2 DEG C/
min；
3. by the Co after step 2. middle roast3O4/ OM-MgO solid powders are fully ground rear standby；
（4）By Co3O4/ OM-MgO is sufficiently mixed with the aqueous solution containing Enrofloxacin, is transferred in brown shaking flask；
（5）Add single persulfate：Single persulfate is added to step（4）In brown shaking flask in carry out the drop of Enrofloxacin
Solution reaction；It is the min of water-bath concussion reaction 30 ~ 120 under conditions of 20 ~ 50 DEG C to keep reacting liquid temperature, is capable of achieving grace promise in water
The efficient removal of Sha Xing, and obtain containing Co3O4The mixed solution of/OM-MgO；
（6）Co is reclaimed using centrifugation or filter type3O4/ OM-MgO, the Co of recovery3O4/ OM-MgO ethanol and deionized water are anti-
Multiple cleaning at least 5 times, and in 60 DEG C of vacuum drying, the Co being recycled3O4/OM-MgO。
2. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（1）1. the mould described in
The quality of plate SBA-15, sucrose and aqueous sulfuric acid is 1：1.25：5.14 g；The mass concentration of the aqueous sulfuric acid is
2.72%。
3. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（1）2. the sugarcane described in
The quality that the mass concentration of sugar aqueous solution is is 19.56%, and the solid powder A is 2.39 with the mass ratio of aqueous sucrose solution：
1.25。
4. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（1）Consolidating described in 4.
Body powder B is 1 with the mass ratio of the NaOH aqueous solution：100~200.
5. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（2）1. described in
The inventory of CMK-3 solid powders is 50g/LMg (NO3)2·6H2O solution, described Mg (NO3)2·6H2The molar concentration of O is
0.25 mol/L。
6. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（3）1. the OM- described in
MgO、Co(NO3)3The mol ratio of 6H2O is 5:1, described Co (NO3)3The molar concentration of 6H2O- ethanol solutions is 0.5
mol/L。
7. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（4）Described in Co3O4/
The dosage of OM-MgO is 10 ~ 500 mg/L aqueous solution containing Enrofloxacin.
8. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（4）Described in containing grace
Promise sand star concentration of aqueous solution is 1 ~ 20 mg/L.
9. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（5）Described in single mistake
Sulfate is selected from least one in Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium.
10. the method for going antibacterials in water removal as claimed in claim 1, it is characterised in that step（5）Described in single mistake
Sulfate is 10 ~ 200 with the mol ratio of Enrofloxacin in the aqueous solution：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611144333.7A CN106732604A (en) | 2016-12-13 | 2016-12-13 | The method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611144333.7A CN106732604A (en) | 2016-12-13 | 2016-12-13 | The method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106732604A true CN106732604A (en) | 2017-05-31 |
Family
ID=58880552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611144333.7A Pending CN106732604A (en) | 2016-12-13 | 2016-12-13 | The method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732604A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246365A (en) * | 2018-01-24 | 2018-07-06 | 上海易明建设工程发展有限公司 | A kind of dark catalyst nanocomposite and its preparation method and application |
| CN109876848A (en) * | 2019-03-11 | 2019-06-14 | 南京大学 | A kind of confinement type CoCNx@C composite catalyst and its preparation method and application |
| CN110116019A (en) * | 2019-04-28 | 2019-08-13 | 太原理工大学 | A kind of nano-cobaltic-cobaltous oxide/aluminium oxide@carried catalyst and its preparation method and application |
| CN111530466A (en) * | 2020-05-11 | 2020-08-14 | 湖南大学 | Method for removing antibiotics in water body by using catalyst activated permonosulfate prepared from waste lithium batteries |
| CN113101940A (en) * | 2021-04-25 | 2021-07-13 | 山西中科国蕴环保科技有限公司 | Catalyst for activating persulfate and method for treating sewage by using catalyst |
| CN114950435A (en) * | 2022-06-21 | 2022-08-30 | 阜阳师范大学 | Preparation method of cobalt-oxygen catalyst, product and application thereof |
| CN115571968A (en) * | 2022-10-12 | 2023-01-06 | 生态环境部南京环境科学研究所 | By using Co 2+ Method for removing 2-chlorophenol in wastewater by catalyzing PMS |
-
2016
- 2016-12-13 CN CN201611144333.7A patent/CN106732604A/en active Pending
Non-Patent Citations (5)
| Title |
|---|
| J.ROGGENBUCK ET AL.: "Ordered Mesoporous Magnesium Oxide with High Thermal Stability Synthesized by Exotemplating Using CMK-3 Carbon", 《J.AM.CHEM.SOC》 * |
| SHINAE JUN ET AL.: "Synthesis of New, Nanoporous Carbon with Hexagonally Ordered Mesostructure", 《J.AM.CHEM.SOC》 * |
| TANYA TSONCHEVA ET AL.: "Cobalt-modified mesoporous MgO, ZrO2, and CeO2 oxides as catalysts for methanol decomposition", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| WEI ZHANG ET AL.: "Supported cobalt oxide on MgO：Highly efficient catalysts for degradation of organic dyes in dilute solutions", 《APPLIED CATALYSIS B:ENVIRONMENTAL》 * |
| 郭洪光等: ""热激活过硫酸盐降解水中典型氟喹诺酮抗生素分析"", 《饮用水安全控制技术会议暨中国土木工程学会水工业分会给水专业委员会第14届年会论文集》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246365A (en) * | 2018-01-24 | 2018-07-06 | 上海易明建设工程发展有限公司 | A kind of dark catalyst nanocomposite and its preparation method and application |
| CN108246365B (en) * | 2018-01-24 | 2020-08-28 | 上海易明建设工程发展有限公司 | Dark catalyst nano composite material and preparation method and application thereof |
| CN109876848A (en) * | 2019-03-11 | 2019-06-14 | 南京大学 | A kind of confinement type CoCNx@C composite catalyst and its preparation method and application |
| CN110116019A (en) * | 2019-04-28 | 2019-08-13 | 太原理工大学 | A kind of nano-cobaltic-cobaltous oxide/aluminium oxide@carried catalyst and its preparation method and application |
| CN110116019B (en) * | 2019-04-28 | 2022-02-25 | 太原理工大学 | Nano cobaltosic oxide/alumina @ carrier catalyst and preparation method and application thereof |
| CN111530466A (en) * | 2020-05-11 | 2020-08-14 | 湖南大学 | Method for removing antibiotics in water body by using catalyst activated permonosulfate prepared from waste lithium batteries |
| CN113101940A (en) * | 2021-04-25 | 2021-07-13 | 山西中科国蕴环保科技有限公司 | Catalyst for activating persulfate and method for treating sewage by using catalyst |
| CN114950435A (en) * | 2022-06-21 | 2022-08-30 | 阜阳师范大学 | Preparation method of cobalt-oxygen catalyst, product and application thereof |
| CN115571968A (en) * | 2022-10-12 | 2023-01-06 | 生态环境部南京环境科学研究所 | By using Co 2+ Method for removing 2-chlorophenol in wastewater by catalyzing PMS |
| CN115571968B (en) * | 2022-10-12 | 2024-03-08 | 生态环境部南京环境科学研究所 | Co utilization 2+ Method for removing 2-chlorophenol in wastewater by catalyzing PMS |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732604A (en) | The method for going antibacterials in water removal using order mesoporous MgO-Supported cobaltosic oxide activation Potassium peroxysulfate | |
| CN101804338B (en) | Process for producing nano titanium dioxide/diatomite composite photocatalytic material | |
| CN105727901B (en) | A kind of preparation method of optically catalytic TiO 2 sorbing material | |
| CN104923230B (en) | A kind of titanium dioxide/ferriferrous oxide nano composite material and preparation method thereof | |
| CN103537237A (en) | Preparation method of Fe3O4@C@PAM core-shell magnetic nano material | |
| CN106277048B (en) | A kind of method and system for preparing anatase titanium dioxide for raw material using titanium slag | |
| CN103962149B (en) | The heterogeneous ozonation solid catalyst of water treatment prepared by rare earth containing zeolite waste residue | |
| CN107744806A (en) | A kind of preparation method of catalyst using expanded graphite as carrier catalysis ozone decomposition | |
| CN106423272A (en) | Supported titanium dioxide/graphene oxide pellets and preparation method and application thereof | |
| CN102295308A (en) | Method for preparing zinc oxide by using zinc-containing waste liquid as raw material | |
| CN105013500B (en) | Heterogeneous fenton catalyst of degrading azoic dye waste water and its production and use | |
| CN103084154B (en) | The method of one Yeasts amalgamation method regenerated carbon | |
| CN102625777B (en) | The manufacture of electroplating sludge process and nano-level iron oxide compound | |
| CN104525173A (en) | Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and TiO2 | |
| CN103894236A (en) | Ceramsite carrier applicable to fenton fluidized bed and having catalytic action, preparation method and application of carrier | |
| CN108773851A (en) | A method of recycling titanium dioxide from discarded SCR catalyst | |
| CN106430699B (en) | It is a kind of to utilize MnxCo3-xO4The method that nanocages activate antiepileptic in single persulfate processing water | |
| CN106430516B (en) | A method of antibacterials in single persulfate degradation water are activated based on the order mesoporous cobaltosic oxide of Fe2O3 doping | |
| CN104724815B (en) | Using MnOx15 PMS compound systems of/SBA efficiently quickly remove peace for neighbour method and application | |
| CN102502812B (en) | Method for preparing octahedral nano titanium dioxide | |
| CN108187707B (en) | Modified steel slag and preparation method and application thereof | |
| CN103521208A (en) | Photocatalyst preparation method | |
| CN108114720A (en) | A kind of preparation method of heterogeneous smooth Fenton catalysis material | |
| CN105879890B (en) | Magnetic composite photocatalyst and its preparation method and application | |
| CN106345417A (en) | Method for preparing material for removing and adsorbing heavy metal lead in wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |