CN113842956B - Preparation method and application of carbon-based encapsulated cobalt oxide magnetic material - Google Patents
Preparation method and application of carbon-based encapsulated cobalt oxide magnetic material Download PDFInfo
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- CN113842956B CN113842956B CN202111267352.XA CN202111267352A CN113842956B CN 113842956 B CN113842956 B CN 113842956B CN 202111267352 A CN202111267352 A CN 202111267352A CN 113842956 B CN113842956 B CN 113842956B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 96
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 77
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000696 magnetic material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 90
- 239000010865 sewage Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010893 paper waste Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 12
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 239000010431 corundum Substances 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 47
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 47
- 230000005389 magnetism Effects 0.000 claims description 13
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 13
- 239000003344 environmental pollutant Substances 0.000 claims description 10
- 231100000719 pollutant Toxicity 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004806 packaging method and process Methods 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
- 238000005406 washing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002386 leaching Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 31
- 230000015556 catabolic process Effects 0.000 description 30
- 239000000523 sample Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000010791 quenching Methods 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- -1 sulfate radical Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- 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
- B01J23/75—Cobalt
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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)
- Catalysts (AREA)
Abstract
The invention belongs to the field of environmental protection, and particularly relates to a preparation method and application of a carbon-based encapsulated cobalt oxide magnetic material. The preparation method comprises the following steps: step one, pretreatment of carbon-based materials: waste paper is selected as a raw material, sheared, immersed in absolute ethyl alcohol for ultrasonic treatment and then dried. And step two, preparing cobalt ion solution. Step three, dipping treatment: immersing the dried material in the solution prepared in the step two. Step four, drying treatment: and leaching and drying the impregnated material. Step five, high-temperature calcination: placing the materials in the step into a corundum ark, calcining for 2 hours in a tube furnace at 600-800 ℃, taking nitrogen as a protective atmosphere in the calcining process, and collecting a calcined product to obtain the required carbon-based encapsulated cobalt oxide magnetic material. The prepared material is used for treating sewage containing TCH, and solves the problems that the cobalt-based catalyst material has high production cost, is easy to separate out a large amount of cobalt ions during use and cannot be recycled.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a preparation method of a carbon-based encapsulated cobalt oxide magnetic material, the carbon-based encapsulated cobalt oxide magnetic material prepared by the method, application of the material in sewage treatment, and a sewage treatment method using tetracycline hydrochloride pollutants.
Background
Tetracycline hydrochloride (TCH) as a broad spectrumAntibiotics are widely used in the fields of medical treatment, animal husbandry, etc. However, excessive use of tetracycline hydrochloride can result in significant residuals in natural water and soil environments, which can severely disrupt the water ecological balance and jeopardize human health. In recent years, advanced oxidation technology based on Peroxomonosulfate (PMS) has been capable of generating sulfate radical (SO) with strong oxidizing power, wide pH application range and long free radical life 4 ·- ) Has been widely used in sewage treatment studies of various organic pollutants including TCH.
Some special catalysts can activate the purification treatment efficiency of PMS during sewage treatment. Wherein Co is 2+ Is the metal ion with highest PMS activating efficiency at present, and Co is provided in use at present 2+ Is mainly a homogeneous catalyst. However, the conventional cobalt-based homogeneous catalyst is difficult to recycle in the use process, so that the use cost is high. In addition, conventional homogeneous catalysts can precipitate Co in large amounts during use 2+ The method comprises the steps of carrying out a first treatment on the surface of the Resulting in Co in treated sewage 2+ Is excessive, co of high concentration 2+ And can pose a serious threat to the environment or human health.
Therefore, it is necessary to develop a recyclable heterogeneous cobalt-based catalyst. Although partial heterogeneous cobalt-based catalysts have been reported in recent years to be applied to sewage treatment, most catalyst materials still have high production cost, complex preparation process and low yield, and Co is easy to appear in the using process of the product 2+ Precipitation problem.
Disclosure of Invention
The invention provides a preparation method and application of a carbon-based encapsulated cobalt oxide magnetic material, aiming at solving the problems that the existing cobalt-based catalyst material has high production cost, is easy to separate out a large amount of cobalt ions during use and cannot be recycled.
The invention is realized by adopting the following technical scheme:
a preparation method of a carbon-based encapsulated cobalt oxide magnetic material comprises the following steps:
step one, pretreatment of carbon-based materials:
selecting waste paper as a carbon-based raw material, and shearing the waste paper into sheets with a specified shape and size; then immersing in absolute ethyl alcohol for ultrasonic treatment for not less than 30min, taking out and drying after ultrasonic treatment is finished.
Step two, preparing cobalt ion impregnating solution:
co (NO) 3 ) 2 ·6H 2 O or CoCl 2 ·6H 2 O is dissolved in deionized water to prepare Co 2+ The solution with the concentration of 0.1mol/L is used as the cobalt ion impregnating solution required by the subsequent steps.
Step three, dipping treatment:
immersing the pretreated carbon-based raw material in the first step into the cobalt ion impregnating solution prepared in the second step, and impregnating at normal temperature for not less than 3 hours.
Step four, drying treatment:
and draining the impregnated carbon-based raw material until the surface does not contain solution, and drying at the temperature of not higher than 60 ℃ to obtain the dried cobalt-containing carbon-based raw material.
Step five, high-temperature calcination:
calcining the cobalt-containing carbon-based raw material in the previous step at the constant temperature of 600-800 ℃ for 2 hours, taking nitrogen as a protective atmosphere in the calcining process, and collecting calcined products according to different calcining temperatures, wherein the calcined products are the required carbon-based encapsulated cobalt oxide magnetic material.
Preferably, in the first step, the waste paper is selected as the express packaging paper, and the sheared size is 1X 2cm 2 。
Preferably, in both the first and fourth steps, the drying temperature during the drying process is set to 60 ℃.
Preferably, in step two, co (NO 3 ) 2 ·6H 2 O is used as raw material to prepare the needed cobalt ion impregnating solution.
Preferably, in the fifth step, the detailed steps of the high temperature calcination process are as follows:
the invention also comprises a carbon-based encapsulated cobalt oxide magnetic material which is prepared by adopting the preparation method. Carbon-based encapsulated cobalt oxideThe macro structure of the magnetic material is sheet-shaped or block-shaped; the material has magnetism; the microstructure of the material is a 3D network structure, co is uniformly distributed on the surface and in the gaps of the 3D network structure 2+ 。
The invention also comprises the application of the carbon-based encapsulated cobalt oxide magnetic material, namely: the carbon-based encapsulated cobalt oxide magnetic material is used as an active catalyst when the peroxymonosulfate is used for purifying tetracycline hydrochloride sewage; and magnetic separation recovery and reuse are carried out on the carbon-based encapsulated cobalt oxide material after the sewage treatment is finished.
The invention also comprises a sewage treatment method containing tetracycline hydrochloride pollutants, wherein the carbon-based encapsulated cobalt oxide magnetic material prepared by the preparation method is used in the treatment process of the sewage treatment method; the sewage treatment method comprises the following steps:
s1: and detecting the concentration of tetracycline hydrochloride in the sewage.
S2: the content ratio of the tetracycline hydrochloride to the carbon-based encapsulated cobalt oxide magnetic material is 50mmol: (0.2-1.0) kg of the carbon-based encapsulated cobalt oxide magnetic material is added into the sewage and uniformly dispersed in the sewage.
S3: the mass ratio of the tetracycline hydrochloride to the peroxymonosulfate is 50mmol: (0.5-1) mol of material ratio, and adding peroxymonosulfate into the sewage; uniformly dispersing the peroxymonosulfate, and reacting for not less than 60 minutes;
s4: after the reaction is finished, the sewage is magnetically absorbed, and the magnetic carbon-based encapsulated cobalt oxide magnetic material with magnetism, which is put into the sewage, is recovered and reused after washing and drying.
As a further improvement of the invention, the cyclic utilization times of the carbon-based encapsulated cobalt oxide magnetic material in the sewage treatment process are not less than 4 times; after each recovery, the material is cleaned for 3 times by clean water or ultrapure water, then the material is dried at the temperature of 60 ℃, and the carbon-based encapsulated cobalt oxide magnetic material is reused after the material is dried.
The technical scheme provided by the invention has the following beneficial effects:
1. the carbon-based encapsulated cobalt oxide magnetic material provided by the invention is a very good pollutant purifying agent and active catalyst. The material can effectively degrade tetracycline hydrochloride contained in sewage; and the PMS can be activated to generate free radicals, so that organic pollutants in sewage can be continuously degraded, and the degradation rate of the PMS on tetracycline hydrochloride and other pollutants is obviously improved.
2. The carbon-based encapsulated cobalt oxide magnetic material provided by the invention is prepared from waste paper and other materials, has a simple preparation process, can effectively reduce the production cost of the material, and further generates good economic value and environmental protection benefit. Meanwhile, the material can be recycled in the use process, and the material has magnetism, so that convenience is provided for recycling the material in the later period. Thereby effectively reducing the material input cost of sewage treatment.
3. The carbon-based encapsulated cobalt oxide magnetic material provided by the invention has a special 3D network microstructure, and can improve the Co of the material 2+ Load ratio and adsorption performance of (a). So as to reduce the Co used by the material while ensuring the activation catalytic performance of the material 2+ The separation rate in the sewage keeps the property of the material stable, and reduces the secondary pollution caused in the water pollution treatment process.
Drawings
Fig. 1 is a flow chart of the steps of a method for preparing a carbon-based encapsulated cobalt oxide magnetic material according to embodiment 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the microstructure of the carbon-based encapsulated cobalt oxide magnetic material prepared in example 1 of the present invention.
Fig. 3 is a scanning electron microscope image of element C in the carbon-based encapsulated cobalt oxide magnetic material prepared in example 1 of the present invention.
Fig. 4 is a scanning electron microscope image of N element in the carbon-based encapsulated cobalt oxide magnetic material prepared in example 1 of the present invention.
Fig. 5 is a scanning electron microscope image of O element in the carbon-based encapsulated cobalt oxide magnetic material prepared in example 1 of the present invention.
Fig. 6 is a scanning electron microscope image of Co element in the carbon-based encapsulated cobalt oxide magnetic material prepared in example 1 of the present invention.
Fig. 7 is an elemental mass spectrum of a carbon-based encapsulated cobalt oxide magnetic material prepared in example 1 of the present invention.
Fig. 8 is a graph comparing the carbon-based encapsulated cobalt oxide magnetic material of example 1 of the present invention before and after TCH degradation.
FIG. 9 is a graph showing the variation of TCH degradation rate of the carbon-based encapsulated cobalt oxide magnetic material calcined at different temperatures in example 2 of the present invention.
FIG. 10 is a graph showing the change in TCH degradation rate when the reagent is used in the quenching test of example 2 of the present invention.
FIG. 11 is a graph showing the variation of TCH degradation rate in the cyclic test of the carbon-based encapsulated cobalt oxide magnetic material of example 2 according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a carbon-based encapsulated cobalt oxide magnetic material, as shown in fig. 1, comprising the following steps:
step one, pretreatment of carbon-based materials:
waste paper is selected as a carbon-based raw material, and specifically, in the embodiment, a waste packaging paper bag used for express documents is used as a raw material. In other embodiments, other document paper, filter paper, corrugated paper, paper express boxes, etc. may also be selected as desired. The pulp raw material and thickness of the used waste paper have a certain influence on the properties of the final product, and comparison tests show that the waste paper express box in the embodiment has the best product performance when being used as the raw material.
In this embodiment, the waste paper is also cut into sheets of prescribed shape and size; the shearing process is mainly used for crushing materials, and the volume is reduced; of materialsThe shape and the size mainly need to be adapted to the post treatment process flow, so that the specification of the produced product can be controlled conveniently; the contact area of the material and sewage can be improved in the application process of later sewage treatment and the like, and the recycling is convenient. Specifically, in this example, waste paper was uniformly sheared to 1X 2cm 2 Strip-shaped sheet of specification. Immersing the sheared paper sheet in absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, taking out after the ultrasonic treatment is finished, and drying at 60 ℃.
Step two, preparing cobalt ion impregnating solution:
in this example, cobalt nitrate hexahydrate was used as the cobalt salt starting material, and 1.22g of Co (NO 3 ) 2 ·6H 2 O is dissolved in 40mL of deionized water to obtain cobalt nitrate solution for standby.
The cobalt nitrate hexahydrate used in this step may alternatively be cobalt chloride hexahydrate in other embodiments, both of which may result in a product with a type of functionality. However, in combination with the comparative test, it was found that the cobalt nitrate hexahydrate used in this example produced a final product with better overall properties than cobalt chloride hexahydrate.
Step three, dipping treatment:
and (3) completely immersing the paper sheet dried in the first step into the cobalt nitrate solution prepared in the second step, and keeping the temperature for 3 hours at normal temperature, so that chloride ions in the cobalt chloride solution fully and uniformly permeate into the paper sheet.
Step four, drying treatment:
and removing the impregnated paper, draining the paper until the surface of the paper does not contain the solution, and drying at the temperature of not higher than 60 ℃ to obtain the dried cobalt-containing carbon-based raw material.
Step five, high-temperature calcination:
(1) Placing the dried cobalt-containing carbon-based raw material into a corundum ark; then, the corundum ark is sent into a tube furnace, and nitrogen is introduced into the tube furnace for 5-10min; completely discharging the air in the tube furnace.
(2) Starting the tube furnace for heating, setting the heating rate of the tube furnace to be 2 ℃/min, preserving heat and calcining for 2 hours after the temperature in the furnace is increased to the preset calcining temperature, and then naturally cooling the tube furnace.
(3) When the temperature in the tube furnace is reduced to room temperature, opening the tube furnace, taking out the corundum ark, and obtaining a calcined product, namely the required carbon-based encapsulated cobalt oxide magnetic material.
Wherein the preset calcination temperature of the tube furnace is 600 ℃, 700 ℃ or 800 ℃ respectively. And collecting the calcined products according to different calcining temperatures, wherein the obtained calcined products are respectively recorded as CoO x /P-600、CoO x /P-700、CoO x and/P-800, wherein the number is marked as the calcination temperature.
The carbon-based encapsulated cobalt oxide magnetic material prepared by the preparation method of the embodiment has a macroscopic structure in a sheet shape or a block shape, the specific shape is related to the use of raw materials, and the sheared waste paper shells are used as raw materials in the embodiment, so that the prepared material is in a sheet shape. The material prepared in the embodiment has obvious magnetism through detection, the magnetism of the material is related to a large amount of cobalt elements contained in the material, and the magnetic strength of the material reflects the content of the cobalt elements in the material to a certain extent. And the microstructure of the material is a 3D network structure. Co is uniformly distributed on the surface and in the gaps of the 3D reticular structure 2+ 。
In order to verify the properties of the material prepared in this example, the test personnel also observe the carbon-based encapsulated cobalt oxide magnetic material prepared in this example under a Scanning Electron Microscope (SEM), so as to obtain microscopic electron micrographs as shown in fig. 2, and as can be seen from the photographs in fig. two, the material has a distinct 3D network structure.
Meanwhile, as shown by analyzing the scanning electron microscope images of the C element, N element and O element of the carbon-based encapsulated cobalt oxide magnetic material in fig. 3-5, it can be found that the 3D network structure in the product in this embodiment is formed by the C element, and the material is prepared from an organic material containing rich C, N, O elements, rather than a pure inorganic carbon skeleton.
The Co element scanning electron microscope of fig. 6 further illustrates: in the carbon-based encapsulated cobalt oxide magnetic material produced in this example, co 2+ Uniformly dispersed on the surface of the carbon skeletonAmong the pores thereof, the impregnation and calcination processes in the preparation method are described such that Co ions are uniformly supported on the carbon base.
The present example also analyzed the elemental composition of the material to obtain an elemental mass spectrum as shown in fig. 7, which verifies the above analysis conclusion from another point of view. Namely; the material obtained in this example uses a carbon matrix as a skeleton, and the Co element is successfully loaded on the carbon matrix.
The carbon-based encapsulated cobalt oxide magnetic material provided by the embodiment can be applied to degradation of tetracycline hydrochloride. Specifically, the prepared carbon-based encapsulated cobalt oxide magnetic material is used as an active catalyst when the peroxymonosulfate purifies tetracycline hydrochloride-containing sewage, and the carbon-based encapsulated cobalt oxide material is subjected to magnetic separation recovery and reutilization after the sewage treatment is finished.
In order to verify the ability of the carbon-based encapsulated cobalt oxide magnetic material provided in this example to purify tetracycline hydrochloride contaminants, the following test was made in this example:
a tetracycline hydrochloride solution was prepared at a concentration of 50. Mu. Mol/L and placed in a clear sample vial. Then adding a proper amount of the carbon-based encapsulated cobalt oxide magnetic material prepared in the embodiment into a sample bottle according to the feeding ratio of 0.2 mg/mL; meanwhile, adding the peroxymonosulfate into the sample bottle according to the concentration ratio of 0.5mmol/L, and taking a photo before the reaction after uniformly stirring. The contents of the sample bottle were reacted for 60min. A second photograph is taken and then a comparison of the first photograph and the second photograph is made as shown in fig. 8.
FIG. 8 includes two parts, the sample bottle of the left half reflecting the state before the sewage degradation treatment. The right half of the sample bottle reflects the state after 60 minutes of treatment with the carbon-based encapsulated cobalt oxide magnetic material provided in this example as an active catalyst.
As can be seen from FIG. 8, the wastewater containing tetracycline hydrochloride was pale yellow before the test, and transparent after the degradation treatment for 60min. It can thus be concluded that: when the carbon-based encapsulated cobalt oxide magnetic material catalyst is provided in the embodiment, the degradation process of tetracycline hydrochloride can be completed rapidly and fully within 60 minutes. Therefore, the product of the embodiment is proved to have the effect of effectively catalyzing and improving the degradation of the tetracycline hydrochloride.
In addition, in the embodiment, in order to verify whether the material provided in the embodiment can be recovered by magnetic separation after purifying sewage; a magnet is also placed near the vial. From the information in the figure, it can be found that the carbon-based encapsulated cobalt oxide magnetic material in the sample bottle is indeed adsorbed on the inner wall of the sample bottle by the magnet. It can thus be demonstrated that: the carbon-based encapsulated cobalt oxide magnetic material provided by the embodiment has obvious magnetism, and also has magnetism after being used, and can be magnetically separated, adsorbed and recovered.
Meanwhile, in this embodiment, the magnetic adsorption test is performed on the treated sewage, and the results in the figure can at least illustrate the following two points: 1. the carbon-based encapsulated cobalt oxide magnetic material after sewage treatment still has magnetism, namely the cobalt element content in the material is still rich; this illustrates to some extent that the material in this example has less elution of cobalt element in the catalytic water purification process. 2. Considering that the material still has stronger magnetism, namely the cobalt element content in the material is rich, the material can be recycled after being recycled.
Example 2
This example provides a method for treating wastewater containing tetracycline hydrochloride contaminants, wherein carbon-based encapsulated cobalt oxide magnetic material prepared as in example 1 was used in the treatment process of the wastewater treatment method.
The sewage treatment method provided by the embodiment comprises the following steps:
s1: and detecting the concentration of tetracycline hydrochloride in the sewage.
S2: the content ratio of the tetracycline hydrochloride to the carbon-based encapsulated cobalt oxide magnetic material is 50mmol: (0.2-1.0) kg of the carbon-based encapsulated cobalt oxide magnetic material is added into the sewage and uniformly dispersed in the sewage.
S3: the mass ratio of the tetracycline hydrochloride to the peroxymonosulfate is 50mmol: (0.5-1) mol of material ratio, and adding peroxymonosulfate into the sewage; uniformly dispersing the peroxymonosulfate, and reacting for not less than 60 minutes;
s4: after the reaction is finished, the sewage is magnetically absorbed, and the magnetic carbon-based encapsulated cobalt oxide magnetic material with magnetism, which is put into the sewage, is recovered and reused after washing and drying.
In order to verify the technical effect of carbon-based encapsulated cobalt oxide magnetic materials in degradation tests, the present example formulated the following control test 1:
four equal volumes of 50. Mu. Mol/L tetracycline hydrochloride solution (TCH) were taken as sample solutions, sample group 1, sample group 2, sample group 3 and sample group 4, respectively. Four equal mass portions of carbon-based encapsulated cobalt oxide magnetic materials (hereinafter referred to as materials) prepared at different calcination temperatures, respectively material 1CoO, were prepared x P-600, material 2: coO (CoO) x P-700, material 3: coO (CoO) x P-800; and 1mmol/L of a Peroxomonosulfate (PMS) solution, and the material was added to the sample solution and then the PMS solution was added during the experiment. And counting the proportion of the residual concentration of the tetracycline hydrochloride in the sample solution to the original concentration within 60min, and drawing a corresponding concentration change curve.
The group information of each sample group is shown in table 1, and the test results are shown in fig. 9.
Table 1: group information table in control test 1
Analysis of the concentration profile in fig. 9 can reveal that: (1) By analyzing other sample groups by taking the sample group 4 as a control group, it can be proved that the PMS solution provided in the embodiment can degrade HCT when being used alone, but after being matched with a material serving as a catalyst, the degradation effect of HCT is obviously improved, the degradation rate is accelerated, and the degradation rate (removal rate) of the final pollutant is obviously improved, and the degradation rate is improved from 40% to 80-90%. (2) Comparing the sample groups 1-3 with each other to obtain materials at different calcining temperaturesCalcining the material at 800 ℃ to obtain material CoO x P-800 has significantly higher degradation rate and degradation rate than the other two groups. And it can be found that the maximum degradation rate can be reached basically in each sample group at 20min, the degradation treatment time is shortened to 20min, and the degradation rate is fast.
To analyze the reaction pathways of the materials in this example for catalysis, this example also performed quench test 2. In the quenching test 2, the same TCH solution, PMS solution as in the control test 1 were used as the sample solution and the purification material, and the material 3 verified to have the best effect was selected as the catalytic material; and two groups of samples, sample group 5 and sample group 6, were set for the test, and methanol (MeOH) solution and tert-butanol (TBA) solution were used as quenchers in the respective sample groups. In the test process, the proportion of the residual concentration of the tetracycline hydrochloride in the sample solution to the original concentration is counted in 60min, and a corresponding concentration change curve is drawn.
The group information of each sample group is shown in table 2, and the sample group 3 in the control test 1 is used as the control group of the quenching test 2, and the test results of the sample groups 5 and 6 are combined to draw a schematic diagram of the change of the tetracycline hydrochloride concentration shown in fig. 10.
Table 2: group information table in quench test 2
Analysis of the concentration profile in fig. 10 can reveal that: the degradation effect of tetracycline hydrochloride in the control group is better than that of the sample group 5 and the sample group 6, and the catalytic effect of the material is partially inhibited but is not completely disappeared under the two quenching conditions. This shows that the process of degrading TCH by the magnetic material has sulfate radical and hydroxyl radical to play a dominant role (methyl alcohol can quench sulfate radical and hydroxyl radical; tertiary butyl alcohol quenches hydroxyl radical).
To verify that the materials in this example were catalytically clean of TCH during multiple recyclesVariation of chemical properties the following cycle test 3 is specified in this example. In the cycle test 3, the same TCH solution, PMS solution as in the control test 1 were used as the sample solution and the purification material, and CoO was used x P-800 as a catalytic material; the catalytic material was recovered after each test was completed, and after the recovery was washed 3 times with ultrapure water, it was put into an oven to be dried at 60 ℃ and then used as the catalytic material for the next round of the cycle test. In each cycle test, the proportion of the residual concentration of the tetracycline hydrochloride of the solution to the original concentration in 60min is counted, and a corresponding concentration change curve is drawn, wherein the cycle number of the cycle test is set to be 4, and the obtained test result is shown in fig. 11.
The analytical test results show that the material in the embodiment can reach almost the same degradation rate for TCH pollutants in multiple cycle tests, and the degradation rate is close to 90%. However, as the cycle number increases, the degradation rate of the material to contaminants decreases, and in the first cycle test, the maximum degradation rate can be reached only for 20 minutes, but as the cycle number increases, the maximum degradation rate for 20 minutes decreases to about 70%. But it is emphasized that: even though the contaminant degradation rate of the material is reduced, the degradation rate is not reduced. This illustrates that the materials provided by this embodiment have good recyclability. Meanwhile, after the material is recycled for a plurality of times, the degradation rate of pollutants is reduced, but the catalytic effect of the material is still considerable, and the material has good practical value.
In summary, the carbon-based encapsulated cobalt oxide magnetic material provided by the embodiment is a very good active catalyst, and can effectively catalyze and improve the degradation efficiency of tetracycline hydrochloride in sewage, activate PMS to generate free radicals, continuously degrade organic pollutants in sewage, and further obviously improve the degradation rate of PMS on tetracycline hydrochloride and other pollutants.
Meanwhile, the carbon-based encapsulated cobalt oxide magnetic material provided by the embodiment is prepared from waste paper and other materials, has a simple preparation process, can effectively reduce the production cost of the material, and further generates good economic value and environmental protection benefit. Meanwhile, the material can be recycled in the use process, and the material has magnetism, so that convenience is provided for recycling the material in the later period. Thereby effectively reducing the material input cost of sewage treatment.
The special 3D network microstructure of the carbon-based encapsulated cobalt oxide magnetic material provided by the embodiment improves the Co of the material 2+ Load ratio and adsorption performance of (a); so as to reduce the Co used by the material while ensuring the activation catalytic performance of the material 2+ The separation rate in the sewage keeps the property of the material stable, and reduces the secondary pollution to the sewage. Therefore, the encapsulated cobalt oxide magnetic material provided by the embodiment has the characteristics of green, economy and environmental friendliness.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the carbon-based encapsulated cobalt oxide magnetic material is characterized by comprising the following steps of:
step one, pretreatment of carbon-based materials:
selecting waste paper as a carbon-based raw material, selecting express packaging paper by using the waste paper, and cutting the waste paper into sheets with specified shapes and sizes; immersing in absolute ethyl alcohol, carrying out ultrasonic treatment for not less than 30min, taking out and drying after ultrasonic treatment is finished;
step two, preparing cobalt ion impregnating solution:
co (NO) 3 ) 2 ·6H 2 O or CoCl 2 ·6H 2 O is dissolved in deionized water to prepare Co 2+ A solution with the concentration of 0.1mol/L is used as cobalt ion impregnating solution required by the subsequent step;
step three, dipping treatment:
immersing the pretreated carbon-based raw material in the first step in the cobalt ion impregnating solution prepared in the second step, and impregnating at normal temperature for not less than 3 hours;
step four, drying treatment:
draining the impregnated carbon-based raw material until the surface does not contain solution, and drying at the temperature of not higher than 60 ℃ to obtain a dried cobalt-containing carbon-based raw material;
step five, high-temperature calcination:
calcining the cobalt-containing carbon-based raw material in the previous step at the constant temperature of 600-800 ℃ for 2 hours, taking nitrogen as a protective atmosphere in the calcining process, and collecting calcined products according to different calcining temperatures in a classified manner, wherein the calcined products are the required carbon-based encapsulated cobalt oxide magnetic material.
2. The method for preparing the carbon-based encapsulated cobalt oxide magnetic material according to claim 1, wherein: in the first step, the sheared waste paper has a size of 1X 2cm 2 。
3. The method for preparing the carbon-based encapsulated cobalt oxide magnetic material according to claim 1, wherein: in the first and fourth steps, the drying temperature in the drying process is set to be 60 ℃.
4. The method for preparing the carbon-based encapsulated cobalt oxide magnetic material according to claim 1, wherein: in step two, co (NO 3 ) 2 ·6H 2 O is used as raw material to prepare the needed cobalt ion impregnating solution.
5. The method for preparing the carbon-based encapsulated cobalt oxide magnetic material according to claim 1, wherein: in the fifth step, the first step is to carry out the process,
the detailed steps of the high temperature calcination process are as follows:
(1) Placing the dried cobalt-containing carbon-based raw material into a corundum ark; then, the corundum ark is sent into a tube furnace, and nitrogen is introduced into the tube furnace for 5-10min; completely exhausting air in the tube furnace;
(2) Starting a tube furnace for heating, setting the heating rate of the tube furnace to be 2 ℃/min, preserving heat and calcining for 2 hours after the temperature in the furnace is increased to a preset calcining temperature, and then naturally cooling the tube furnace;
(3) When the temperature in the tube furnace is reduced to room temperature, opening the tube furnace, taking out the corundum ark, and obtaining a calcined product, namely the required carbon-based encapsulated cobalt oxide magnetic material.
6. The method for preparing the carbon-based encapsulated cobalt oxide magnetic material according to claim 1, wherein: the preset calcination temperature of the tube furnace is 600 ℃, 700 ℃ or 800 ℃ respectively.
7. A carbon-based encapsulated cobalt oxide magnetic material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 6;
the carbon-based encapsulated cobalt oxide magnetic material macrostructure is sheet-shaped or block-shaped; the material has magnetism; the microstructure of the material is a 3D network structure, co is uniformly distributed on the surface and in the gaps of the 3D network structure 2+ 。
8. Use of a carbon-based encapsulated cobalt oxide magnetic material according to claim 7, wherein: the carbon-based encapsulated cobalt oxide magnetic material is used as an active catalyst when the peroxymonosulfate is used for purifying tetracycline hydrochloride sewage; and carrying out magnetic separation recovery and reutilization on the carbon-based encapsulated cobalt oxide material after the sewage treatment is finished.
9. A sewage treatment method containing tetracycline hydrochloride pollutants is characterized by comprising the following steps: a carbon-based encapsulated cobalt oxide magnetic material prepared by the preparation method according to any one of claims 1 to 6 in the treatment process of a sewage treatment method; the sewage treatment method comprises the following steps:
s1: detecting the concentration of tetracycline hydrochloride in the sewage;
s2: the content ratio of the tetracycline hydrochloride to the carbon-based encapsulated cobalt oxide magnetic material is 50mmol: (0.2-1.0 kg of the carbon-based encapsulated cobalt oxide magnetic material is added into the sewage and uniformly dispersed in the sewage;
s3: the mass ratio of the tetracycline hydrochloride to the peroxymonosulfate is 50mmol: (0.5-1) mol of material ratio, and adding peroxymonosulfate into the sewage; uniformly dispersing the peroxymonosulfate, and reacting for not less than 60 minutes;
s4: after the reaction is finished, the sewage is magnetically absorbed, and the magnetic carbon-based encapsulated cobalt oxide magnetic material with magnetism, which is put into the sewage, is recovered and reused after washing and drying.
10. The method for treating the sewage containing tetracycline hydrochloride pollutants as defined in claim 9, wherein: the recyclable frequency of the carbon-based encapsulated cobalt oxide magnetic material in the sewage treatment process is not less than 4 times; after each recovery, cleaning the material for 3 times by using clear water or ultrapure water, then drying the material at the temperature of 60 ℃, and reutilizing the carbon-based encapsulated cobalt oxide magnetic material after drying.
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