CN115532293A - Preparation method and application of nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst - Google Patents
Preparation method and application of nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst Download PDFInfo
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- CN115532293A CN115532293A CN202211128884.XA CN202211128884A CN115532293A CN 115532293 A CN115532293 A CN 115532293A CN 202211128884 A CN202211128884 A CN 202211128884A CN 115532293 A CN115532293 A CN 115532293A
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- 239000011347 resin Substances 0.000 title claims abstract description 129
- 229920005989 resin Polymers 0.000 title claims abstract description 129
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000010355 oscillation Effects 0.000 claims abstract description 21
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 20
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 20
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 18
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 2
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- 238000003917 TEM image Methods 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
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Images
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
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- 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 relates to the technical field of composite carbon materials and advanced catalytic oxidation in environmental management, and particularly discloses a preparation method and application of a nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst, which comprises the following steps: placing the waste D001 resin in a container, adding ethanol, placing in a shaking table for oscillation, and pouring out the ethanol; repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin; pouring waste D001 resin into the prepared metal cobalt ion solution, putting the solution into a shaking table for oscillation, pouring out the solution and draining residual liquid; adding dicyandiamide, and uniformly stirring; and (3) placing the waste D001 resin into a tubular furnace, and calcining under the protection of nitrogen to obtain the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst. The preparation method disclosed by the invention is simple, low in cost, mild in synthesis conditions, high in resource degree, convenient for solid-liquid separation, recoverable and reusable, and beneficial to large-scale popularization.
Description
Technical Field
The invention relates to the technical field of composite carbon materials and advanced catalytic oxidation in environmental management, in particular to a preparation method and application of a nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst.
Background
At present, the conventional advanced oxidation technology AOPs uses OH generated with strong oxidizing effect to oxidize and degrade organic pollutants, and SO is used in comparison with OH advanced oxidation technology 4 - The basic advanced oxidation technology has the advantages of strong oxidation capacity, good oxidant stability, high oxidant utilization rate and wide applicable PH, and receives more attention in the aspect of removing the refractory organic pollutants, SO 4 - Is obtained from activated persulfate PS and peroxymonosulfate PMS, and PMS is a nontoxic and multifunctional oxidant, i.e. potassium hydrogen persulfate complex salt (2 KHSO) 5 ·KHSO 4 ·K 2 SO 4 ) The main active components of the catalyst are activated by heat, activated by ultraviolet light, activated by carbon materials and excited and activated by sulfide or oxide of transition metal, wherein the capability of the transition metal for activating PMS is high-efficiency and rapid, so that the transition metal catalyst is a hotspot for researching the degradation of pollutants in water by catalyzing PMS.
The sulfur element can generate a plurality of positive effects in the reaction process of Fenton or similar Fenton, and common transition metals such as iron, cobalt, copper, manganese and the like have positive effects on H 2 O 2 Has certain catalytic activity with PMS, and the research on transition metal sulfide focuses on the utilization of its reducing property or the application of transition metal sulfide in electrocatalytic hydrogen production, so that various transition metal sulfides can be used as a novel catalytic material to effectively catalyze and activate H 2 O 2 Or PMS degrades organic pollutants in water, and sulfur element has stronger electronegativity and forms a compound with transition metal, so that the stability is better, and in addition, the sulfur element and the transition metal form a compoundThe sulfur mineral has rich storage, so the sulfur mineral is used as an efficient, green and economic environmental catalyst, and has wide practical application prospect.
In order to enable the catalyst to play a larger role in practical engineering application and control the cost of the catalyst per se, the carbon material has lower price compared with metal oxide and also has specific surface area, which is beneficial to the adhesion of the metal oxide, sulfide and the like, the nitrogen-doped carbon material has wide application in the field of catalytic research by unique properties, a defect site and nitrogen species can be introduced in the nitrogen doping process, five available valence electrons in nitrogen enable the doped carbon to form a strong covalent bond, which is beneficial to the interaction of metal carriers, and the nitrogen species can improve the dispersion degree and stability of active components such as metal and the like, so that the catalytic performance is improved, the basic constituent elements of D001 cation exchange resin are C, S, O, H and the like, wherein the contents of C and S are high, the waste resin is low in price and wide in source, if the carbon material can be prepared as a raw material, a certain amount of metal cobalt is adsorbed by the strong cation exchange property of the carbon material, and then the carbon material is mixed with the nitrogen-containing component for co-thermal calcination to prepare the carbon material with a new nitrogen-doped metal-based carbon material, so that the treatment cost of the ion exchange resin is reduced.
Disclosure of Invention
The invention aims to provide a preparation method and application of a nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst, and aims to solve the technical problems of high cost, complex synthetic method and material loss in the preparation process of the catalyst in the prior art.
In order to achieve the purpose, the preparation method of the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst comprises the following steps:
placing waste D001 resin in a container, adding ethanol, placing in a shaking table for oscillation at 25 ℃, pouring out ethanol after shaking uniformly, and adding pure water for washing twice;
repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin;
pouring the waste D001 resin into the prepared metal cobalt ion solution, placing the solution into a shaking table for oscillation at 25 ℃, pouring out the solution after oscillation is carried out uniformly, and draining residual liquid;
placing the waste D001 resin into a mortar, adding dicyandiamide, grinding and stirring uniformly by using a grinding rod or a medicine spoon, placing the mixture into a square boat, standing and drying;
wrapping the waste D001 resin by using tinfoil, placing the wrapped waste D001 resin in a tubular furnace, and calcining the wrapped waste D001 resin under the protection of nitrogen to obtain the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst.
Wherein, when the steps 1 to 3 are carried out, the solid-to-liquid ratio is 1g: 5-20 ml, the shaking table oscillation speed is 120-180 r/min, and the oscillation time is 1-2 h.
Wherein the molar weight of the supported cobalt ions in the metal cobalt ion solution is 0-2 mmol per gram of the waste D001 resin.
Wherein the molar weight of the dicyandiamide is 0-10 mmol per gram of the waste D001 resin, and the waste D001 resin is kept standing for 0-6 h at the room temperature.
Wherein the calcining temperature of the tubular furnace is 550-650 ℃, and the calcining time is 4-6 h.
The invention also provides application of the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst prepared by the preparation method of the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst, which is applied to activating PMS (permanent magnet system) to degrade organic pollutants in waste water, wherein the waste water comprises printing and dyeing waste water, pharmaceutical waste water, antibiotic waste water, chemical waste water, washing waste water and urban domestic sewage.
The preparation method and the application of the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst have the beneficial effects that:
the waste cation exchange resin is used as a matrix, cobalt ions are adsorbed through the high-efficiency adsorption and ion exchange effects of the waste cation exchange resin and then are mixed with dicyandiamide for co-heating, and finally the carbon sphere catalyst material for efficiently activating PMS is formed through sintering, so that the treatment and resource utilization of the waste D001 resin are realized, the great loss of the cobalt ions in the material preparation process is greatly reduced, the activity of the prepared catalyst material is also superior to that of a carbon sphere material prepared by loading the waste D001 resin with single metal cobalt, and the waste recycling is also realized while the organic pollutants in the waste water are efficiently degraded.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a flow chart of the steps of example 1 of the preparation method of the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst of the present invention.
Fig. 2 is a flowchart of the steps of example 2 of the method for preparing the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst.
Fig. 3 is a flowchart of the steps of example 3 of the method for preparing the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst.
Fig. 4 is a flowchart of the steps of example 4 of the method for preparing the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst.
Fig. 5 is an XRD chart of the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst prepared in example 1 according to the present invention.
FIG. 6 is an SEM image of nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst prepared in example 1.
FIG. 7 is a TEM image of nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst prepared in example 1 according to the present invention.
FIG. 8 is an XPS plot of nitrogen-doped cobalt-supported spent resin-based carbon sphere catalysts prepared in example 1 according to the present invention.
FIG. 9 is a graph showing that PMS activated by nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst prepared in example 1 degrades bronofen.
Detailed Description
The invention provides a preparation method of a nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst, which comprises the following steps of:
placing waste D001 resin in a container, adding ethanol, placing in a shaking table for oscillation at 25 ℃, pouring out ethanol after shaking uniformly, and adding pure water for washing twice;
repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin;
pouring the waste D001 resin into the prepared metal cobalt ion solution, placing the solution into a shaking table for oscillation at 25 ℃, pouring out the solution after oscillation and shaking uniformly, and draining residual liquid;
placing the waste D001 resin into a mortar, adding dicyandiamide, grinding and stirring uniformly by using a grinding rod or a medicine spoon, placing the mixture into a square boat, standing and drying;
wrapping the waste D001 resin by using tinfoil, placing the wrapped waste D001 resin in a tubular furnace, and calcining the wrapped waste D001 resin under the protection of nitrogen to obtain the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst.
When the steps 1 to 3 are carried out, the solid-liquid ratio is 1g: 5-20 ml, the shaking table oscillation speed is 120-180 r/min, and the oscillation time is 1-2 h.
The molar weight of the supported cobalt ions in the metal cobalt ion solution is 0-2 mmol per gram of the waste D001 resin.
The molar weight of the dicyandiamide is 0-10 mmol per gram of the waste D001 resin, and the waste D001 resin is kept stand for 0-6 h at the room temperature.
The calcining temperature of the tubular furnace is 550-650 ℃, and the calcining time is 4-6 h.
The invention also provides application of the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst prepared by the preparation method of the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst, which is applied to the degradation of organic pollutants in waste water by activated PMS (permanent magnet system), wherein the waste water comprises printing and dyeing waste water, pharmaceutical waste water, antibiotic waste water, chemical waste water, washing waste water and urban domestic sewage.
Embodiment 1, referring to fig. 1, the present invention further provides a method for preparing a nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst, including the following steps:
s1: placing waste D001 resin in a container, adding ethanol, placing in a shaking table for oscillation at 25 ℃, pouring out ethanol after shaking uniformly, and adding pure water for washing twice;
s2: repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin;
s3: mixing 1g of the cleaned waste D001 resin with 20ml of cobalt nitrate, placing the cobalt nitrate with the molar mass of 0.75mmol in a shaking table at 25 ℃ for shaking for 2 hours, pouring out the solution after shaking uniformly, and draining residual liquid;
s4: placing the waste D001 resin into a mortar, adding 5mmol of dicyandiamide, grinding and stirring uniformly by using a grinding rod or a medicine spoon, placing the mixture into a square boat, standing for 3 hours, and drying;
s5: wrapping the waste D001 resin by using tinfoil, placing the wrapped waste D001 resin in a tubular furnace, and calcining the wrapped waste D001 resin at 550 ℃ for 6 hours under the protection of nitrogen to obtain the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst.
s1: placing the waste D001 resin into a container, adding ethanol, placing into a shaking table for oscillation at 25 ℃, pouring out the ethanol after shaking uniformly, and adding pure water for washing twice;
s2: repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin;
s3: mixing 1g of the cleaned waste D001 resin with 20ml of cobalt nitrate, placing the cobalt nitrate with the molar mass of 0.75mmol in a shaking table at 25 ℃ for shaking for 1 hour, pouring out the solution after shaking uniformly, and draining residual liquid;
s4: placing the waste D001 resin into a mortar, adding 3mmol dicyandiamide, grinding and stirring uniformly by using a grinding rod or a medicine spoon, placing the mixture into a square boat, standing for 6 hours, and drying;
s5: wrapping the waste D001 resin by using tinfoil, placing the wrapped waste D001 resin in a tubular furnace, and calcining the wrapped waste D001 resin at 550 ℃ for 6 hours under the protection of nitrogen to obtain the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst.
Embodiment 3, referring to fig. 3, the present invention further provides a method for preparing a nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst, including the following steps:
s1: placing waste D001 resin in a container, adding ethanol, placing in a shaking table for oscillation at 25 ℃, pouring out ethanol after shaking uniformly, and adding pure water for washing twice;
s2: repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin;
s3: mixing 1g of the cleaned waste D001 resin with 20ml of cobalt nitrate, placing the cobalt nitrate with the molar mass of 1.0mmol in a shaking table at 25 ℃ for shaking for 1 hour, pouring out the solution after shaking uniformly, and draining residual liquid;
s4: placing the waste D001 resin into a mortar, adding 3mmol dicyandiamide, grinding and stirring uniformly by using a grinding rod or a medicine spoon, and placing into a square boat for drying;
s5: and wrapping the waste D001 resin by using tinfoil, placing the wrapped resin in a tubular furnace, and calcining for 6 hours at 600 ℃ under the protection of nitrogen to obtain the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst.
Embodiment 4, referring to fig. 4, the present invention further provides a method for preparing a nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst, including the following steps:
s1: placing waste D001 resin in a container, adding ethanol, placing in a shaking table for oscillation at 25 ℃, pouring out ethanol after shaking uniformly, and adding pure water for washing twice;
s2: repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin;
s3: mixing 1g of the cleaned waste D001 resin with 20ml of cobalt nitrate, placing the cobalt nitrate with the molar mass of 1.0mmol in a shaking table at 25 ℃ for 2 hours, shaking uniformly, pouring out the solution, and draining the residual liquid;
s4: placing the waste D001 resin into a mortar, adding 5mmol of dicyandiamide, grinding and stirring uniformly by using a grinding rod or a medicine spoon, placing the mixture into a square boat, standing for 4 hours, and drying;
s5: and wrapping the waste D001 resin by using tinfoil, placing the wrapped resin in a tubular furnace, and calcining for 6 hours at 650 ℃ under the protection of nitrogen to obtain the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst.
Through the verification of the final effects of the four embodiments, with the preparation method of embodiment 1, the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst prepared by doping 5mmol dicyandiamide with 0.75mmol cobalt ion per gram of the waste D001 resin is optimal, under the conditions that the addition amount is 0.3g/L, the concentration of PMS is 0.7mmol/L and the temperature is 25 ℃, a catalytic degradation test is performed on 50ml of 10mg/L nondegradable pollutant bronife, the reaction device is a constant temperature oscillator and a conical flask, and the removal rate of a water sample is calculated through the measurement of a high performance liquid chromatograph, and the degradation curve in fig. 9 shows that the removal rate of the single PMS and the single resin and the catalytic action of the single resin and dicyandiamide after high-temperature calcination to bronife in one hour is less than 15%; the catalyst prepared by only loading metal cobalt has more than 70 percent of degradation effect on the bronofine; however, the removal rate of ibuprofen after cobalt is loaded and the mixture of the cobalt and dicyandiamide is subjected to high-temperature co-pyrolysis can reach 95%, so that the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst prepared by the method has the capability of efficiently activating PMS to degrade organic pollutants.
In order to determine the crystal structure of the material, XRD research is carried out, and an XRD pattern of a carbon sphere type catalyst material prepared by mixing 0.75mmol of cobalt-loaded waste resin per gram of waste resin, cobalt-loaded waste resin and dicyandiamide and carrying out high-temperature calcination is respectively shown in figure 5, and as can be seen from the XRD pattern, all carbon sphere materials have typical carbon peaks around 20 degrees; after the single waste resin is carbonized, the characteristic diffraction peaks of magnesium oxide appear at diffraction angles of 42.9 degrees and 62.4 degrees respectively, and the diffraction peaks respectively correspond to the diffraction peaks of a standard card JCPDS:45-0946 crystal planes and (200) and (220) crystal planes of the material prepared by loading metallic cobalt, wherein diffraction peaks at the two positions are greatly weakened, and the condition that the calcium and magnesium ions in the resin can be replaced by the cobalt ions in the process of impregnating the cobalt ions is indicated, and diffraction peaks of cobalt sulfide appear at diffraction angle positions of 30.5 degrees, 35.2 degrees, 47.7 degrees and 54.5 degrees respectively, wherein the diffraction peaks correspond to the diffraction peaks of a standard card JCPDS:42-0826, and the mixed calcination of cobalt-loaded waste resin and dicyandiamide shows that the diffraction peak positions of the cobalt-loaded waste resin and the dicyandiamide are the same as those of a material prepared by loading cobalt alone, and the diffraction peaks of cobalt sulfide appear at the diffraction angle positions of 30.5 degrees, 35.2 degrees, 47.7 degrees and 54.5 degrees respectively, but the peak shapes become narrower and sharper.
Fig. 6 is a 1000-fold enlarged view (2 um scale) of the surface of a carbon sphere material obtained after sintering waste resin, cobalt-loaded waste resin and cobalt-nitrogen co-doped waste resin, respectively, and it can be seen from fig. a that a large amount of strip-shaped and blocky objects are attached to the surface of the waste resin after high-temperature sintering, which may be that metal calcium and magnesium form a metal composite with a resin component during sintering; the surface of the graph b is relatively clean, and only a few small particles and blocks formed by clustering the small particles are present, compared with carbon spheres sintered from waste resin, long-strip-shaped objects and blocks can not be seen almost, and the number of the small particles is greatly reduced, which shows that after cobalt ions are impregnated, on one hand, calcium and magnesium ions can be replaced by the cobalt ions, on the other hand, the cobalt ions enter the resin in a large amount and are mainly distributed in the resin through sintering, so that the cobalt ions have strong cation exchange performance.
Fig. 7 shows a transmission scanning electron microscope (TEM) image of a carbon sphere material obtained after sintering waste resin, cobalt-loaded waste resin and cobalt-nitrogen co-doped waste resin, which can be clearly seen under transmission scanning shooting, wherein a large number of black dots are distributed on the images b and c, and the number of the black dots in the image a is far less than that of the black dots in the image b, which may be that metal cobalt successfully forms a corresponding metal compound on the resin, and the image c is darker than the black dots in the image b, which indicates that the compound formed by cobalt on the resin is higher in purity or better in crystallinity.
In order to determine approximate estimation of the valence state and content of the element of the prepared cobalt sulfide supported nitrogen doped carbon sphere type catalyst, an X-ray photoelectron spectroscopy (XPS) characterization is carried out, a graph a in FIG. 8 shows a main binding energy peak value of various elements possibly existing in a carbon sphere type composite material through a measurement spectrum, b-f respectively correspond to valence state binding energy partial peaks of several main elements of carbon nitrogen oxygen sulfur cobalt in the material, a graph b shows that the peak value mainly exists in the form of carbon-carbon bond, the binding energy possibly exists in the form of carbon-sulfur bond or carbon-nitrogen bond at 285.3eV, the binding energy possibly corresponds to a small number of carbon-oxygen bonds at other binding energy positions according to the position and area of each binding energy peak of C1s, a graph C can clearly see that the N1s peak has characteristic peaks with binding energies of 398.1eV, 399eV and 400.3eV, which respectively correspond to pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, the content is not too large, the nitrogen element mainly exists in the form of pyrrole nitrogen and graphite nitrogen according to a graph d shows that the peak value of the element oxygen spectrum shows that the peak area is larger than the carbon-nitrogen surface area, and the oxygen absorption peak area can be shown in the graph 532The presence of attached oxygen, C-S or C-SO respectively at 164eV, 165eV and 167.8eV of the binding energy in the graph e x And the presence of negative divalent sulfur at binding energies of 161.9eV and 163.2eV respectively corresponds to S2p 3/2 And S2p 1/2 F is a diffraction peak at several different binding energy positions of cobalt, wherein the binding energy positions are satellite peaks generated by emitting X-rays when 802eV and 785.1eV are possible as samples, and the Co2p at the binding energy positions of 778.5eV and 780.8eV and 793.6eV and 797.0eV are respectively 3/2 And Co2p 1/2 Spin-orbital trivalent cobalt and divalent cobalt, and comparing peak areas, it can be found that the main valence state of cobalt is divalent, and combining with the XPS peak diagram of sulfur, it can be proved that cobalt ions adsorbed on the resin are finally sintered on the carbon spheres mainly in the form of cobalt sulfide.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. The preparation method of the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst is characterized by comprising the following steps of:
placing waste D001 resin in a container, adding ethanol, placing in a shaking table for oscillation at 25 ℃, pouring out ethanol after shaking uniformly, and adding pure water for washing twice;
repeating the step of washing with alcohol for 1-2 times, and drying the waste D001 resin;
pouring the waste D001 resin into the prepared metal cobalt ion solution, placing the solution into a shaking table for oscillation at 25 ℃, pouring out the solution after oscillation is carried out uniformly, and draining residual liquid;
placing the waste D001 resin into a mortar, adding dicyandiamide, grinding and stirring uniformly by using a grinding rod or a medicine spoon, placing the mixture into a square boat, standing and drying;
and wrapping the waste D001 resin by using tinfoil, placing the wrapped resin in a tubular furnace, and calcining the wrapped resin under the protection of nitrogen to obtain the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst.
2. The method for preparing the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst as claimed in claim 1,
when the steps 1 to 3 are carried out, the solid-liquid ratio is 1g: 5-20 ml, the shaking table oscillation speed is 120-180 r/min, and the oscillation time is 1-2 h.
3. The method for preparing the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst as claimed in claim 2,
the molar weight of the supported cobalt ions in the metal cobalt ion solution is 0-2 mmol per gram of the waste D001 resin.
4. The method for preparing the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst as claimed in claim 3,
the molar weight of the dicyandiamide is 0-10 mmol per gram of the waste D001 resin, and the waste D001 resin is kept stand for 0-6 h at the room temperature.
5. The method for preparing the nitrogen-doped cobalt-supported waste resin-based carbon sphere catalyst as claimed in claim 4,
the calcining temperature of the tubular furnace is 550-650 ℃, and the calcining time is 4-6 h.
6. The application of the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst prepared by the preparation method of the nitrogen-doped cobalt-loaded waste resin-based carbon sphere catalyst as claimed in any one of claims 1 to 5,
the method is applied to the activated PMS to degrade organic pollutants in wastewater, wherein the wastewater comprises printing and dyeing wastewater, pharmaceutical wastewater, antibiotic wastewater, chemical wastewater, washing wastewater and urban domestic sewage.
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