CN110180573B - Heterogeneous magnetic catalyst CoFeO prepared by using anode material of waste battery2Method of @ CN and use thereof - Google Patents
Heterogeneous magnetic catalyst CoFeO prepared by using anode material of waste battery2Method of @ CN and use thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000010405 anode material Substances 0.000 title claims abstract description 18
- 239000002699 waste material Substances 0.000 title abstract description 6
- CAOOISJXWZMLBN-PPHPATTJSA-N htn0d03vrz Chemical compound Cl.C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 CAOOISJXWZMLBN-PPHPATTJSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000010926 waste battery Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 67
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 229910021645 metal ion Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 230000001502 supplementing effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000005389 magnetism Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical group [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
The invention discloses a method for preparing a heterogeneous magnetic catalyst CoFeO by using a waste battery anode material2Method of @ CN and application thereof, which utilizes anode material of waste battery as raw material and obtains Co-containing material by dissolving the material2+And Fe3+To Fe3+The CoFeO is prepared by a hydrothermal method2Then CoFeO is added2Calcining the mixture of the catalyst and melamine to obtain a heterogeneous magnetic catalyst CoFeO2@ CN. By using a synthetic heterogeneous magnetic catalyst CoFeO2@ CN catalyzes PMS to degrade levofloxacin hydrochloride, and four parameters such as temperature, catalyst dosage, PMS concentration, initial pH value and the like are optimized in the reaction process. Heterogeneous magnetic catalyst CoFeO2@ CN is a magnetic catalyst prepared by taking waste battery materials as raw materials, and embodies the waste recycling principle and the advantage of recycling and reusing the materials.
Description
Technical Field
The invention belongs to a heterogeneous magnetic catalytic material CoFeO2The technical field of synthesis of @ CN and degradation of antibiotic levofloxacin hydrochloride thereof, and particularly relates to a method for preparing a heterogeneous magnetic catalyst CoFeO by using a waste battery anode material2@ CN and methods of use thereof.
Background
Advanced oxidation techniques (AOPs) are recognized as a novel water treatment technique for degrading recalcitrant pollutants by highly reactive free radicals, most commonly sulfate free radicals (SO)4 •-）。PMS（2KHSO5·KHSO4·K2SO4) Is a potassium hydrogen peroxydisulfate compound salt, and the active substance is potassium hydrogen monoperoxydisulfate KHSO5Due to an SO3 −The unique structure of asymmetric peroxide formed by substituting HOOH makes the peroxide easy to excite to generate a large amount of SO4 •-. Catalyzing PMS to generate SO4 •-The system is an oxidation system similar to a Fenton reagent, and transition metal Fe2+、Co2+Isoenergetic catalysis PMS generates a large amount of active SO with strong oxidizing capability and no selectivity4 •-Free radicals are used for thoroughly oxidizing organic pollutants in water into CO2、H2O and inorganic salts.
Pharmaceutical and Personal Care Products (PPCPs) have high durability, bioaccumulation and ecotoxicity and are difficult to degrade, and thus have been under much attention. At present, the most studied PPCPs are antibiotics, and levofloxacin hydrochloride (LVF) is widely and frequently applied to various fields of medicine due to broad-spectrum sterilization, but the traditional water treatment technology cannot be effectively removed due to long half-life period, and the levofloxacin hydrochloride is discharged into a water environment along with the wastewater after the traditional biological treatment, so that potential harm to public health exists, and the PPCPs are widely concerned. Waste battery materials belong to dangerous waste, and more serious secondary heavy metal pollution is caused by improper disposal; the insoluble magnetic catalyst is synthesized by utilizing waste battery materials, and the technical problem can be well solved.
Disclosure of Invention
The invention solves the technical problem of providing a heterogeneous magnetic catalyst CoFeO prepared by using a waste battery anode material2Method of @ CN and application thereof, and heterogeneous magnetic catalyst CoFeO prepared by method2The oxidation system composed of @ CN and PMS can be effectiveDegrading levofloxacin hydrochloride and heterogeneous magnetic catalyst CoFeO2The @ CN can be recycled and reused, and the catalytic activity is still high, so that secondary pollution to the environment is avoided, and waste is reduced.
The invention adopts the following technical scheme to solve the technical problems, and the heterogeneous magnetic catalyst CoFeO is prepared by using the anode material of the waste battery2The method of @ CN is characterized by comprising the following specific steps:
step S1: after the waste battery is disassembled, dissolving the anode material in a mixed solution of sulfuric acid and hydrogen peroxide with a volume ratio of 1:9, wherein the solid-to-liquid ratio is 50g/L, filtering with a filter membrane, and collecting filtrate to obtain the Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2: supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+The molar ratio of (1: 1) and the total molar amount of metal ions is 1.0mol, citric acid with the same total molar amount as the metal ions is added into the solution at 60 ℃, the solution is stirred, ammonia water is used for adjusting the pH value of a mixed system to be 8.0, the mixed system is stirred for 10 hours, then suspension is transferred into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene for reaction for 12 hours at 200 ℃, and after cooling, centrifugation, washing and drying are carried out to obtain CoFeO2；
Step S3: 10-30mg of the CoFeO produced2Dispersing in 50mL deionized water, carrying out ultrasonic treatment for 10min, adding 100mg melamine into the suspension, carrying out ultrasonic treatment on the mixed system for 1h, then placing the mixed system in a drying oven at 65 ℃ for drying, placing the dried sample in a tubular furnace, and calcining at 600 ℃ for 2h to obtain CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 9-23 wt%2@CN。
The invention relates to a method for preparing a heterogeneous magnetic catalyst CoFeO by using a waste battery anode material2The method of @ CN is characterized by comprising the following specific steps:
step S1: after the waste battery is disassembled, the anode material is dissolved in sulfuric acid and sulfuric acid with the volume ratio of 1:9In 10wt% hydrogen peroxide solution with solid-to-liquid ratio of 50g/L, filtering with filter membrane, and collecting filtrate to obtain Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2: supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+The molar ratio of (1: 1) and the total molar amount of metal ions is 1.0mol, citric acid with the same total molar amount as the metal ions is added into the solution at 60 ℃, the solution is stirred, ammonia water is used for adjusting the pH value of a mixed system to be 8.0, the mixed system is stirred for 10 hours, then suspension is transferred into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene for reaction for 12 hours at 200 ℃, and after cooling, centrifugation, washing and drying are carried out to obtain CoFeO2；
Step S3: 15mg of CoFeO thus obtained was added2Dispersing in 50mL deionized water, carrying out ultrasonic treatment for 10min, adding 100mg melamine into the suspension, carrying out ultrasonic treatment on the mixed system for 1h, then placing the mixed system in a drying oven at 65 ℃ for drying, placing the dried sample in a tubular furnace, and calcining at 600 ℃ for 2h to obtain CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 13wt%2@CN。
The heterogeneous magnetic catalyst CoFeO of the invention2The application of @ CN in catalyzing PMS to degrade levofloxacin hydrochloride is characterized by comprising the following specific steps: at room temperature, under the condition of initial pH value of the solution, 5mL of 0.01 mol.L-1PMS solution of (1) and 15mg CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 13wt%2The oxidation system consisting of @ CN was added to 100mL of 10 mg. L-1In the levofloxacin hydrochloride water solution, the mixed system is placed on a magnetic stirrer to be stirred and degraded for 50min, the degradation efficiency of the levofloxacin hydrochloride is 89.4 percent, and a heterogeneous magnetic catalyst CoFeO2@ CN is recycled. The subsequent cycle experiment results show that the catalytic degradation effects are respectively 77.98%, 77.17%, 75.65% and 74.55%, so that the heterogeneous magnetic catalyst CoFeO2@ CN is recyclable and has good recyclability.
The method firstly utilizes the anode material of the waste battery as the raw material, and obtains the material containing Co by dissolving the material2+And Fe3 +To Fe3+The CoFeO is prepared by a hydrothermal method2. Then CoFeO is added2Calcining the mixture of the catalyst and melamine to obtain a heterogeneous magnetic catalyst CoFeO2@ CN. By using a synthetic heterogeneous magnetic catalyst CoFeO2@ CN catalyzes PMS to degrade levofloxacin hydrochloride, and four parameters such as temperature, catalyst dosage, PMS concentration, initial pH value and the like are optimized in the reaction process. Heterogeneous magnetic catalyst CoFeO2@ CN is a magnetic catalyst prepared by taking waste battery materials as raw materials, and embodies the waste recycling principle and the advantage of recycling and reusing the materials.
Drawings
FIG. 1 shows the CoFeO, a heterogeneous magnetic catalyst, obtained in example 22FLSEM picture of @ CN;
FIG. 2 shows the CoFeO, a heterogeneous magnetic catalyst, prepared in example 22HRSEM image of @ CN;
FIG. 3 shows the CoFeO, a heterogeneous magnetic catalyst, obtained in example 22XPS plot of @ CN.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
【15mg 9wt% CoFeO2@CN+PMS】
Step S1: after the waste battery is disassembled, dissolving the anode material in a mixed solution of sulfuric acid and 10wt% of hydrogen peroxide in a volume ratio of 1:9, wherein the solid-to-liquid ratio is 50g/L, filtering with a filter membrane, and collecting filtrate to obtain the Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2:supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+The molar ratio of (1: 1) and the total molar amount of metal ions is 1.0mol, citric acid with the same total molar amount as the metal ions is added into the solution at 60 ℃, the solution is stirred, ammonia water is used for adjusting the pH value of a mixed system to be 8.0, the mixed system is stirred for 10 hours, then suspension is transferred into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene for reaction for 12 hours at 200 ℃, and after cooling, centrifugation, washing and drying are carried out to obtain CoFeO2；
Step S3: 10mg of CoFeO thus prepared2Dispersing in 50mL deionized water, carrying out ultrasonic treatment for 10min, adding 100mg melamine into the suspension, carrying out ultrasonic treatment on the mixed system for 1h, then placing the mixed system in a drying oven at 65 ℃ for drying, placing the dried sample in a tubular furnace, and calcining at 600 ℃ for 2h to obtain CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 9wt%2@CN。
At room temperature, under the condition of initial pH value of the solution, 5mL of 0.01 mol.L-1PMS solution of (1) and 15mg CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 9wt%2@ CN was added to 100mL of 10 mg. L-1In the aqueous solution of levofloxacin hydrochloride, the degradation rate of levofloxacin hydrochloride reaches 68.75 percent after 50 min.
Example 2
【15mg 13wt% CoFeO2@CN+PMS】
Step S1: after the waste battery is disassembled, dissolving the anode material in a mixed solution of sulfuric acid and 10wt% of hydrogen peroxide in a volume ratio of 1:9, wherein the solid-to-liquid ratio is 50g/L, filtering with a filter membrane, and collecting filtrate to obtain the Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2: supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+At a molar ratio of 1:1 and a total molar amount of metal ions of 1.0mol, adding citric acid in an amount equal to the total molar amount of metal ions to the solution at 60 deg.C, stirring andadjusting the pH value of the mixed system to 8.0 by using ammonia water, stirring the mixed system for 10h, transferring the suspension into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene, reacting for 12h at 200 ℃, cooling, centrifuging, washing and drying to obtain CoFeO2；
Step S3: 15mg of CoFeO thus obtained was added2Dispersing in 50mL deionized water, carrying out ultrasonic treatment for 10min, adding 100mg melamine into the suspension, carrying out ultrasonic treatment on the mixed system for 1h, then placing the mixed system in a drying oven at 65 ℃ for drying, placing the dried sample in a tubular furnace, and calcining at 600 ℃ for 2h to obtain CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 13wt%2@CN。
At room temperature, under the condition of initial pH value of the solution, 5mL of 0.01 mol.L-1PMS solution of (1) and 15mg CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 13wt%2@ CN was added to 100mL of 10 mg. L-1In the aqueous solution of levofloxacin hydrochloride, the degradation rate of levofloxacin hydrochloride reaches 89.4 percent after 50 min.
Example 3
【15mg 17wt% CoFeO2@CN+PMS】
Step S1: after the waste battery is disassembled, dissolving the anode material in a mixed solution of sulfuric acid and 10wt% of hydrogen peroxide in a volume ratio of 1:9, wherein the solid-to-liquid ratio is 50g/L, filtering with a filter membrane, and collecting filtrate to obtain the Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2: supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+The molar ratio of (1: 1) and the total molar amount of metal ions is 1.0mol, citric acid with the same total molar amount as the metal ions is added into the solution at 60 ℃, the solution is stirred, ammonia water is used for adjusting the pH value of a mixed system to be 8.0, the mixed system is stirred for 10 hours, then suspension is transferred into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene for reaction for 12 hours at 200 ℃, and after cooling, centrifugation, washing and drying are carried out to obtain CoFeO2；
Step S3: 20mg of CoFeO produced2Dispersing in 50mL deionized water, carrying out ultrasonic treatment for 10min, adding 100mg melamine into the suspension, carrying out ultrasonic treatment on the mixed system for 1h, then placing the mixed system in a drying oven at 65 ℃ for drying, placing the dried sample in a tubular furnace, and calcining at 600 ℃ for 2h to obtain CoFeO217wt% of heterogeneous magnetic catalyst CoFeO2@CN。
At room temperature, under the condition of initial pH value of the solution, 5mL of 0.01 mol.L-1PMS solution of (1) and 15mg CoFeO217wt% of heterogeneous magnetic catalyst CoFeO2@ CN was added to 100mL of 10 mg. L-1In the levofloxacin hydrochloride water solution, the degradation rate of the levofloxacin hydrochloride reaches 74.66 percent after 50 min.
Example 4
【15mg 23wt% CoFeO2@CN+PMS】
Step S1: after the waste battery is disassembled, dissolving the anode material in a mixed solution of sulfuric acid and 10wt% of hydrogen peroxide in a volume ratio of 1:9, wherein the solid-to-liquid ratio is 50g/L, filtering with a filter membrane, and collecting filtrate to obtain the Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2: supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+The molar ratio of (1: 1) and the total molar amount of metal ions is 1.0mol, citric acid with the same total molar amount as the metal ions is added into the solution at 60 ℃, the solution is stirred, ammonia water is used for adjusting the pH value of a mixed system to be 8.0, the mixed system is stirred for 10 hours, then suspension is transferred into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene for reaction for 12 hours at 200 ℃, and after cooling, centrifugation, washing and drying are carried out to obtain CoFeO2；
Step S3: 30mg of CoFeO thus prepared2Dispersing in 50mL deionized water, performing ultrasonic treatment for 10min, adding 100mg melamine into the suspension, performing ultrasonic treatment for 1h, drying in a 65 ℃ oven, calcining the dried sample in a tube furnace at 600 ℃Sintering for 2h to obtain CoFeO223wt% of heterogeneous magnetic catalyst CoFeO2@CN。
At room temperature, under the condition of initial pH value of the solution, 5mL of 0.01 mol.L-1PMS solution of (1) and 15mg CoFeO223wt% of heterogeneous magnetic catalyst CoFeO2@ CN was added to 100mL of 10 mg. L-1In the levofloxacin hydrochloride water solution, the degradation rate of the levofloxacin hydrochloride reaches 83.61 percent after 50 min.
Example 5
【15mg 13wt% CoFeO2@CN】
0.015g CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 13wt%2@ CN was added to 100mL of 10mg L-1And (3) taking about 5mL of solution out of the levofloxacin hydrochloride aqueous solution at a preset time point by using an injector, passing the solution through a 0.22-micron microporous filter membrane, directly measuring the absorbance under ultraviolet visible light, and calculating the degradation rate of the levofloxacin hydrochloride to 17.78% in 50min according to the measurement result.
Example 6
【PMS】
At 100mL of 10mg L-15mL of 0.01 mol/L levofloxacin hydrochloride aqueous solution is added-1The PMS solution is taken out by an injector at a preset time point, about 5mL of the solution passes through a 0.22 mu m microporous filter membrane, the absorbance is directly measured under ultraviolet visible light, and the degradation rate of the levofloxacin hydrochloride reaches 2.22 percent when the degradation rate is calculated to be 50min according to the measurement result.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (4)
1. Heterogeneous magnetism prepared by using waste battery anode materialCatalyst CoFeO2The method of @ CN is characterized by comprising the following specific steps:
step S1: after the waste battery is disassembled, dissolving the anode material in a mixed solution of sulfuric acid and hydrogen peroxide with a volume ratio of 1:9, wherein the solid-to-liquid ratio is 50g/L, filtering with a filter membrane, and collecting filtrate to obtain the Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2: supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+The molar ratio of (1: 1) and the total molar amount of metal ions is 1.0mol, citric acid with the same total molar amount as the metal ions is added into the solution at 60 ℃, the solution is stirred, ammonia water is used for adjusting the pH value of a mixed system to be 8.0, the mixed system is stirred for 10 hours, then suspension is transferred into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene for reaction for 12 hours at 200 ℃, and after cooling, centrifugation, washing and drying are carried out to obtain CoFeO2；
Step S3: 10-30mg of the CoFeO produced2Dispersing in 50mL deionized water, carrying out ultrasonic treatment for 10min, adding 100mg melamine into the suspension, carrying out ultrasonic treatment on the mixed system for 1h, then placing the mixed system in a drying oven at 65 ℃ for drying, placing the dried sample in a tubular furnace, and calcining at 600 ℃ for 2h to obtain CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 9-23 wt%2@CN。
2. The method for preparing the heterogeneous magnetic catalyst CoFeO by using the anode material of the waste battery as claimed in claim 12The method of @ CN is characterized by comprising the following specific steps:
step S1: after the waste battery is disassembled, dissolving the anode material in a mixed solution of sulfuric acid and 10wt% of hydrogen peroxide in a volume ratio of 1:9, wherein the solid-to-liquid ratio is 50g/L, filtering with a filter membrane, and collecting filtrate to obtain the Co-containing solution2+、Fe3+And SO4 2-The filtrate is subjected to membrane dilution treatment, and then the Co in the solution is measured by an atomic absorption method2+And Fe3+The content of (A);
step S2: supplementing ferric sulfate according to the content of metal ions in the solution so as to enable Co in the solution to be in a state of being added2+And Fe3+The molar ratio of (1: 1) and the total molar amount of metal ions is 1.0mol, citric acid with the same total molar amount as the metal ions is added into the solution at 60 ℃, the solution is stirred, ammonia water is used for adjusting the pH value of a mixed system to be 8.0, the mixed system is stirred for 10 hours, then suspension is transferred into a stainless steel high-pressure reaction kettle of polytetrafluoroethylene for reaction for 12 hours at 200 ℃, and after cooling, centrifugation, washing and drying are carried out to obtain CoFeO2；
Step S3: 15mg of CoFeO thus obtained was added2Dispersing in 50mL deionized water, carrying out ultrasonic treatment for 10min, adding 100mg melamine into the suspension, carrying out ultrasonic treatment on the mixed system for 1h, then placing the mixed system in a drying oven at 65 ℃ for drying, placing the dried sample in a tubular furnace, and calcining at 600 ℃ for 2h to obtain CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 13wt%2@CN。
3. Heterogeneous magnetic catalyst CoFeO prepared by the method according to any one of claims 1-22Application of @ CN in catalyzing PMS to degrade levofloxacin hydrochloride.
4. The heterogeneous magnetic catalyst CoFeO according to claim 32The application of @ CN in catalyzing PMS to degrade levofloxacin hydrochloride is characterized by comprising the following specific steps: at room temperature, under the condition of initial pH value of the solution, 5mL of 0.01 mol.L-1PMS solution of (1) and 15mg CoFeO2Heterogeneous magnetic catalyst CoFeO with weight percentage of 13wt%2The oxidation system consisting of @ CN was added to 100mL of 10 mg. L-1In the levofloxacin hydrochloride water solution, the mixed system is placed on a magnetic stirrer to be stirred and degraded for 50min, the degradation efficiency of the levofloxacin hydrochloride is 89.4 percent, and a heterogeneous magnetic catalyst CoFeO2@ CN is recycled.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582772A (en) * | 2017-01-04 | 2017-04-26 | 中国科学技术大学苏州研究院 | CoFe<2>O<4>/g-C<3>N<4> magnetic nanomaterial and preparation method therefor |
| CN107890869A (en) * | 2017-11-23 | 2018-04-10 | 河南师范大学 | Magnetic carries the preparation method of cobalt ordered mesoporous carbon material and its application in catalysis Oxone degraded Levofloxacin Wastewaters |
| CN107983391A (en) * | 2017-12-14 | 2018-05-04 | 河南师范大学 | Insoluble magnetic cobalt/defective g-C3N4 composite catalysts and its application in Oxone degrading waste waters are catalyzed |
| CN109231979A (en) * | 2018-11-09 | 2019-01-18 | 河南师范大学 | A method of Conjugate ferrite magnetostriction materials are prepared by raw material of waste and old lithium ion battery |
-
2019
- 2019-05-20 CN CN201910420089.XA patent/CN110180573B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582772A (en) * | 2017-01-04 | 2017-04-26 | 中国科学技术大学苏州研究院 | CoFe<2>O<4>/g-C<3>N<4> magnetic nanomaterial and preparation method therefor |
| CN107890869A (en) * | 2017-11-23 | 2018-04-10 | 河南师范大学 | Magnetic carries the preparation method of cobalt ordered mesoporous carbon material and its application in catalysis Oxone degraded Levofloxacin Wastewaters |
| CN107983391A (en) * | 2017-12-14 | 2018-05-04 | 河南师范大学 | Insoluble magnetic cobalt/defective g-C3N4 composite catalysts and its application in Oxone degrading waste waters are catalyzed |
| CN109231979A (en) * | 2018-11-09 | 2019-01-18 | 河南师范大学 | A method of Conjugate ferrite magnetostriction materials are prepared by raw material of waste and old lithium ion battery |
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