CN109482186A - A kind of magnetism concave convex rod class Fenton catalysis material and the preparation method and application thereof - Google Patents
A kind of magnetism concave convex rod class Fenton catalysis material and the preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000005389 magnetism Effects 0.000 title claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 27
- 230000015556 catabolic process Effects 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 239000004098 Tetracycline Substances 0.000 description 19
- 229960002180 tetracycline Drugs 0.000 description 19
- 229930101283 tetracycline Natural products 0.000 description 19
- 235000019364 tetracycline Nutrition 0.000 description 19
- 150000003522 tetracyclines Chemical class 0.000 description 19
- 229960000892 attapulgite Drugs 0.000 description 15
- 229910052625 palygorskite Inorganic materials 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000008236 heating water Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 oxygen radicals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J23/745—Iron
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of magnetic concave convex rod class Fenton catalysis material and the preparation method and application thereof is related to, the catalysis material reduces the pollution of waste using waste as raw material, reduces the preparation cost of composite material；And catalytic activity is high, rate of catalysis reaction is fast.Above-mentioned magnetism concave convex rod class Fenton catalysis material, is mixed by every liter of waste acid liquor and 30~480g concave convex rod.
Description
Technical field
The present invention relates to a kind of Fenton catalysis material and the preparation method and application thereof, especially a kind of magnetic concave convex rod class is fragrant
Pause catalysis material and the preparation method and application thereof.
Background technique
Traditional Fenton technology have been demonstrated can effective degradable organic pollutant, especially in the organic of difficult for biological degradation
In the wastewater treatment of object, high-level oxidation technology obtains preferable development and application.But traditional Fenton technology still has perhaps
More crucial deficiencies, it is wide to have been found applicable pH range for class Fenton technology in recent years, a large amount of sludge will not be generated, so as to keep away
Exempt to generate secondary pollution, is with the technology for well promoting the use prospect.
Summary of the invention
One of the objects of the present invention is to provide a kind of magnetic concave convex rod class Fenton catalysis materials, and the catalysis material is with discarded
Object is raw material, reduces the pollution of waste, reduces the preparation cost of composite material；And catalytic activity is high, rate of catalysis reaction is fast.
To achieve the goals above, technical solution provided by the invention is such that a kind of magnetic concave convex rod class Fenton is urged
Change material, is mixed by every liter of waste acid liquor and 30~480g concave convex rod.
Preferably, the iron-content of the waste acid liquor is 60~120g/L, H+Content is 910mg/L.
The second object of the present invention is to provide the preparation method of above-mentioned magnetic concave convex rod class Fenton catalysis material, the preparation
Method reaction condition is mild, can carry out under normal pressure, without using surfactant and other organic solvents, reduces and prepared
The pollution generated in journey.
To achieve the goals above, technical solution provided by the invention is such that a kind of magnetic concave convex rod as described above
The preparation method of class Fenton catalysis material, concave convex rod is put into waste acid liquor, is stirred, and heating adds precipitating reagent to adjust pH, constant temperature
Sediment is collected in stirring, separation, is washed, dry.
Preferably, the iron-content of the waste acid liquor is 60~120g/L.
Preferably, the H of the waste acid liquor+Content is 900~920mg/L.
Preferably, every liter of waste acid liquor 30~480g concave convex rod.
Preferably, described plus precipitating reagent adjusts pH to 6.0~12.0.
Preferably, the temperature that is heated to is 60~90 DEG C.
Preferably, the constant temperature mixing time is 1~4h.
The third object of the present invention is to provide the application of above-mentioned magnetic concave convex rod class Fenton catalysis material.
To achieve the goals above, technical solution provided by the invention is such that a kind of magnetic concave convex rod as described above
Class Fenton catalysis material is applied to degradation organic pollutants.
The invention has the benefit that
(1) quick separating of the invention in order to realize attapulgite, using iron and steel pickling waste liquid, i.e., in steel manufacture process
The waste liquid that pickling process generates prepares composite material as raw material, and composite material is made to have catalytic performance while having magnetic.
Iron and the feature of concave convex rod respectively are sufficiently combined, the activity of catalyst and the removal efficiency to organic contamination is promoted, accelerates non-
Similar Fenton technology promotes the use.
(2) invention is magnetic recessed using coprecipitation preparation using iron and steel pickling waste liquid and natural attapulgite as raw material
Convex stick class Fenton catalysis material degradation organic pollutants.Prepared material not only overcomes general heterogeneous class Fenton catalysis
Material activity is low, the slower problem of rate of catalysis reaction, and using waste as raw material, realizes to the effective of trade waste
It utilizes, reduces the pollution of waste, reduce the preparation cost of composite material；And reaction condition is mild, can under normal pressure into
Row, without using surfactant and other organic solvents, reduces pollution produced during the preparation process.
(3) the method for the present invention is compared to FeCl3And FeSO4·7H2O is the material of raw material preparation, and preparation cost is more
It is low.
(4) magnetic attapulgite material property prepared by the present invention is stablized, and structure destruction and material are not susceptible in reaction process
Material has magnetism, is easily separated by solid-liquid separation after reaction.
(5) magnetic attapulgite material catalytic activity prepared by the present invention is high, can be catalyzed Fenton's reaction, organic in water of degrading
The rate of pollutant is fast, and can work in wider pH range.
Detailed description of the invention
Fig. 1 is the influence relational graph that different Fe/ concave convex rod mass ratioes prepare that catalysis material degrades to tetracycline；
Fig. 2 is the SEM image of catalysis material prepared by embodiment 2；
Fig. 3 is the TEM image of catalysis material prepared by embodiment 2；
Fig. 4 is the hysteresis loop figure of catalysis material prepared by embodiment 2；
Fig. 5 is different H2O2To the influence relational graph of tetracycline degradation under dosage；
Fig. 6 is under the initial pH of differential responses system to the influence relational graph of tetracycline degradation；
Fig. 7 is magnetic concave convex rod class Fenton catalysis material 2 prepared by embodiment 2 and environment remediation material prepared by comparative example 1
Expect the comparison diagram of B degradation tetracycline.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, but described embodiment
It is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel all other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
Waste acid liquor is taken, concave convex rod is added, stirs total iron in waste acid liquor with concave convex rod mass ratio 1:0.5 magnetic force
It mixes, after heating water bath reaches 80 DEG C, 10min is stirred in water bath with thermostatic control, and precipitating reagent regulation system pH=11, water bath with thermostatic control is added
After stirring 3h, separation obtains sediment, and washing is dry to get magnetic concave convex rod class Fenton catalysis material 1.
Embodiment 2
Waste acid liquor is taken, concave convex rod is added, makes total iron and concave convex rod mass ratio 1:1 in waste acid liquor, magnetic agitation,
After heating water bath reaches 80 DEG C, 10min is stirred in water bath with thermostatic control, and precipitating reagent regulation system pH=11 is added, and water bath with thermostatic control is stirred
After mixing 3h, separation obtains sediment, and washing is dry to get magnetic concave convex rod class Fenton catalysis material 2.
The present embodiment prepares the scanning electron microscope of resulting magnetic concave convex rod class Fenton catalysis material and projection electron microscope is detailed in
Fig. 2-3.By Fig. 2-3 it is found that attapulgite's surface is attached to Fe3O4Nanosphere body particulate particles, nanosphere body particle diameter exist
50nm or so, attapulgite are gathered into bundles in threadiness.The structure of catalysis material is similar to rodlike core-shell structure, and concave-convex surface is not
Flat, material has more reactivity point, and catalytic capability is stronger.
The hysteresis loop figure that the present embodiment prepares resulting magnetic concave convex rod class Fenton catalysis material is detailed in Fig. 4.It can by Fig. 4
Know, catalysis material shows almost zero remanent magnetism and coercivity, shows that brittle material is superparamagnetism, and magnetic concave convex rod is saturated magnetic
Change intensity is 44.13emu g-1, quick separating can be carried out to catalysis material under the action of externally-applied magnetic field.
Embodiment 3
Waste acid liquor is taken, concave convex rod is added, makes total iron and concave convex rod mass ratio 1:2 in waste acid liquor, magnetic agitation,
After heating water bath reaches 80 DEG C, 10min is stirred in water bath with thermostatic control, and precipitating reagent regulation system pH=11 is added, and water bath with thermostatic control is stirred
After mixing 3h, separation obtains sediment, and washing is dry to get magnetic concave convex rod class Fenton catalysis material 3.
Embodiment 4
Waste acid liquor is taken, concave convex rod is added, makes total iron and concave convex rod mass ratio 1:3 in waste acid liquor, magnetic agitation,
After heating water bath reaches 80 DEG C, 10min is stirred in water bath with thermostatic control, and precipitating reagent regulation system pH=11 is added, and 3h is stirred in water bath with thermostatic control
Afterwards, separation obtains sediment, and washing is dry to get magnetic concave convex rod class Fenton catalysis material 4.
Embodiment 5
Waste acid liquor is taken, concave convex rod is added, makes total iron and concave convex rod mass ratio 1:4 in waste acid liquor, magnetic agitation,
After heating water bath reaches 80 DEG C, 10min is stirred in water bath with thermostatic control, and precipitating reagent regulation system pH=11 is added, and water bath with thermostatic control is stirred
After mixing 3h, separation obtains sediment, and washing is dry to get magnetic concave convex rod class Fenton catalysis material 5.
Comparative example 1
Step 1: pretreated attapulgite is used H2O2It is purified, magnetic agitation 5h, ultrasonic disperse frequency is
40kHz, ultrasonic disperse time are 30min, the attapulgite purified.
Step 2: HCl solution is added in the attapulgite of purifying, 5h, ultrasonic disperse 1h are stirred；Drying is washed, is lived
The attapulgite of change.
It is dispersed in 240ml deionized water, magnetic agitation in three-necked flask step 3: weighing 2g activation attapulgite
6h, ultrasonic 30min make to be uniformly dispersed.
Step 4: the NaOH using 0.1M adjusts pH=8, nitrogen is led into attapulgite suspension and carries out aeration
Step 5: by FeSO4And FeCl3It is dissolved in deionized water respectively, obtains 0.6mol/LFeSO4Solution and 0.8mol/
L FeCl3Solution.
Step 6: in a nitrogen atmosphere, in the suspension obtained to the 4th step, 0.6mol/L FeSO is added dropwise in substep4
(20ml) and 0.8mol/L FeCl3(20ml), ultrasound, makes it be uniformly dispersed.
Step 7: in a nitrogen atmosphere, adjusting the 4th step using the NaOH of 0.1M and obtaining Fe3O4The attapulgite of load is mixed
The pH=10 of liquid is closed, and persistently stirs 1.5h in 65 DEG C of water-baths.
Step 8: the Fe that the 5th step is obtained3O4The attapulgite of load, elution, drying, is made the environment remediation
Material B.
Experimental example 1
Embodiment 1-5 is prepared into resulting magnetic concave convex rod class Fenton catalysis material 1-5 and puts into pH according to 0.2g/L respectively
In=7.0 100mg/l tetracycline, then put into 100mM H2O2, at a temperature of 30 ± 1 DEG C under the speed of 250r/min
1h sampling analysis is reacted in shaking table.
Different Fe/ concave convex rod mass ratioes prepare the influence relationship that magnetic concave convex rod class Fenton catalysis material degrades to tetracycline
Figure is detailed in Fig. 1, and the magnetic concave convex rod degradation tetracycline difference on effect of difference Fe/ concave convex rod mass ratio is unobvious as seen from the figure, and four
Ring element degradation rate within the scope of 61-77%, but with concave convex rod ratio increase, degradation effect also decrease to some degree,
It may be due to Fe3O4It is main catalytic specie in composite material；In addition attapulgite loaded Fe3O4, work as Fe3O4Place composite wood
When material ratio is higher, Fe is reduced3O4Agglomeration, so from figure it is known that Fe/ concave convex rod mass ratio in a certain range
Prepared composite material can preferable catalytic degradation tetracycline.
Experimental example 2
Embodiment 2 is prepared into resulting magnetic concave convex rod class Fenton catalysis material 2 and adds to pH=7.0's according to 0.2g/L
In 100mg/L tetracycline, then 40mM is put into respectively, 60mM, 80mM, 100mM H2O2, with 250r/ at a temperature of 30 ± 1 DEG C
1h sampling analysis is reacted under the speed of min in shaking table.
H2O2Dosage is detailed in Fig. 5 to the influence relational graph that tetracycline is degraded, as seen from the figure, with the increasing of hydrogen peroxide dosage
Add, degradation efficiency is promoted from 37% to 76% also with promotion, tetracycline degradation rate, this is because hydrogen peroxide increases in system
Afterwards, catalysis material surface generates more active oxygen radicals and attacks organic pollutant.
Experimental example 3
It embodiment 2 is prepared into resulting magnetic concave convex rod class Fenton catalysis material 2 adds to pH respectively according to 0.2g/L and be
3.0, in 5.0 and 7.0 100mg/L tetracycline, then 100mM H is put into2O2, with 250r/min's at a temperature of 30 ± 1 DEG C
1h sampling analysis is reacted under speed in shaking table.
Initial pH value is detailed in Fig. 6, as seen from the figure, pH value to the influence diagram of magnetic concave convex rod catalysis class Fenton removal organic matter
Being changed 3.0,5.0,7.0 from acid medium to neutral medium, the final removal rate of tetracycline is increased with pH and is reduced, but first
Beginning pH=7.0, tetracycline degradation rate remain to reach nearly 76%, similar research shows that acid medium can promote catalyst surface iron
Ion release, promotes the generation of hydroxyl radical free radical, to there is higher reaction rate, Fig. 6 also illustrates magnetism prepared by the present invention
Concave convex rod is suitable for wider pH value.
Experimental example 4
Magnetic concave convex rod class Fenton catalysis material 2 and ecological restoration material B are added to pH=7.0's according to 0.2g/L respectively
In 100mg/L tetracycline, then put into 100mM H2O2, at a temperature of 30 ± 1 DEG C with the speed of 250r/min under in shaking table
React 1h sampling analysis.Magnetic concave convex rod class Fenton catalysis material 2 and comparative example 1 prepared by embodiment 2 prepares resulting environment
Repair materials B degradation tetracycline comparison diagram is detailed in Fig. 7.As seen from the figure, 2 catalytic degradation tetracycline of catalysis material prepared by the present invention
Effect is better than ecological restoration material B.Ecological restoration material B only has 27.91% in 1h degradation tetracycline efficiency, and prepared by the present invention
Catalysis material 2 degrade tetracycline efficiency close to 76%, and ecological restoration material B preparation process can generate new discarded salt
Acid, and the spent acid in 2 preparation process of catalysis material prepared by the present invention in reasonable utilization iron and steel pickling waste liquid, preparation process ring
It protects, it is more excellent to prepare material catalytic effect.
Claims (10)
1. a kind of magnetism concave convex rod class Fenton catalysis material, which is characterized in that by every liter of waste acid liquor and 30~480g concave convex rod
It mixes.
2. a kind of magnetic concave convex rod class Fenton catalysis material according to claim 1, which is characterized in that the waste acid liquor
Iron-content is 60~120g/L, H+Content is 910mg/L.
3. a kind of preparation method of concave convex rod class Fenton catalysis material magnetic as described in claim 1-2 is any, which is characterized in that
Concave convex rod is put into waste acid liquor, is stirred, heating adds precipitating reagent to adjust pH, constant temperature stirring, and sediment, water are collected in separation
It washes, it is dry.
4. a kind of preparation method of magnetic concave convex rod class Fenton catalysis material according to claim 3, which is characterized in that described
The iron-content of waste acid liquor is 60~120g/L.
5. a kind of preparation method of magnetic concave convex rod class Fenton catalysis material according to claim 3, which is characterized in that described
The H of waste acid liquor+Content is 900~920mg/L.
6. a kind of preparation method of magnetic concave convex rod class Fenton catalysis material according to claim 3, which is characterized in that every liter
Waste acid liquor 30~480g concave convex rod.
7. a kind of preparation method of magnetic concave convex rod class Fenton catalysis material according to claim 3, which is characterized in that described
Precipitating reagent is added to adjust pH to 6.0~12.0.
8. a kind of preparation method of magnetic concave convex rod class Fenton catalysis material according to claim 3, which is characterized in that described
Being heated to temperature is 60~90 DEG C.
9. a kind of preparation method of magnetic concave convex rod class Fenton catalysis material according to claim 3, which is characterized in that described
Constant temperature mixing time is 1~4h.
10. one kind magnetic concave convex rod class Fenton catalysis material as described in claim 1-2 is any is applied to organic dirt in degradation water
Contaminate object.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811200725.XA CN109482186A (en) | 2018-10-16 | 2018-10-16 | A kind of magnetism concave convex rod class Fenton catalysis material and the preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036209A (en) * | 2019-12-12 | 2020-04-21 | 广州润方环保科技有限公司 | Preparation method and application of magnetic kaolin |
| CN111036171A (en) * | 2019-12-12 | 2020-04-21 | 广州润方环保科技有限公司 | Magnetic clay mineral material and preparation method and application thereof |
| CN112624413A (en) * | 2020-12-18 | 2021-04-09 | 中国科学院南京土壤研究所 | Method for simultaneously converting tetracycline organic molecules and trivalent arsenic |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707564A (en) * | 2015-03-16 | 2015-06-17 | 环境保护部南京环境科学研究所 | Preparing method of novel attapulgite and method for treating heavy metal waste water with attapulgite |
| CN106268812A (en) * | 2016-08-25 | 2017-01-04 | 扬州大学 | A kind of nano-magnetic ecological restoration material on the ferroso-ferric oxide load attapulgite removing removal organic polluter and preparation method thereof |
| CN106334518A (en) * | 2016-09-29 | 2017-01-18 | 环境保护部南京环境科学研究所 | Recyclable magnetic phosphorus adsorbent and preparation method thereof |
| CN107021469A (en) * | 2017-03-28 | 2017-08-08 | 华南师范大学 | A kind of utilization spent acid and bagasse prepare BC S Fe/Ni method and its remove the application of nitrate |
-
2018
- 2018-10-16 CN CN201811200725.XA patent/CN109482186A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707564A (en) * | 2015-03-16 | 2015-06-17 | 环境保护部南京环境科学研究所 | Preparing method of novel attapulgite and method for treating heavy metal waste water with attapulgite |
| CN106268812A (en) * | 2016-08-25 | 2017-01-04 | 扬州大学 | A kind of nano-magnetic ecological restoration material on the ferroso-ferric oxide load attapulgite removing removal organic polluter and preparation method thereof |
| CN106334518A (en) * | 2016-09-29 | 2017-01-18 | 环境保护部南京环境科学研究所 | Recyclable magnetic phosphorus adsorbent and preparation method thereof |
| CN107021469A (en) * | 2017-03-28 | 2017-08-08 | 华南师范大学 | A kind of utilization spent acid and bagasse prepare BC S Fe/Ni method and its remove the application of nitrate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036209A (en) * | 2019-12-12 | 2020-04-21 | 广州润方环保科技有限公司 | Preparation method and application of magnetic kaolin |
| CN111036171A (en) * | 2019-12-12 | 2020-04-21 | 广州润方环保科技有限公司 | Magnetic clay mineral material and preparation method and application thereof |
| CN112624413A (en) * | 2020-12-18 | 2021-04-09 | 中国科学院南京土壤研究所 | Method for simultaneously converting tetracycline organic molecules and trivalent arsenic |
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