CN114100634A - Preparation method, product and application of magnetic multi-component iron-carbon composite Fenton-like catalyst - Google Patents
Preparation method, product and application of magnetic multi-component iron-carbon composite Fenton-like catalyst Download PDFInfo
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- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/34—Organic compounds containing oxygen
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- 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
- C02F2101/36—Organic compounds containing halogen
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- 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
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- C02F2305/026—Fenton's reagent
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Abstract
The invention provides a preparation method, a product and application of a magnetic multi-component iron-carbon composite Fenton-like catalyst. The preparation method comprises the following steps: (1) adding a carbon source into a ferrous sulfate aqueous solution, stirring and drying to obtain a precursor; (2) calcining the precursor under the protection of nitrogen to obtain intermediate powder; (3) and (3) acid-washing and activating the intermediate powder to obtain the magnetic multi-component iron-carbon composite catalyst. The preparation method of the magnetic multi-component iron-carbon composite Fenton-like catalyst is simple to operate and easy to realize industrialization. The magnetic multi-component iron-carbon composite Fenton-like catalyst prepared by the preparation method is high in catalytic activity, can effectively improve the pollutant degradation rate and is stable in performance when being applied to the process of degrading organic pollutants through catalytic oxidation, can be quickly separated through an external magnetic field, and is simple to operate, low in cost, wide in pH application range and high in practical value.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method, a product and application of a magnetic multi-component iron-carbon composite Fenton-like catalyst.
Background
The rapid development of modern industry and the discharge of large amounts of waste water into the environment, especially some of the recalcitrant organic pollutants, have brought great challenges to traditional sewage treatment systems. The fenton oxidation technology can degrade various organic matters by generating hydroxyl radicals with strong oxidizing property, and is considered as one of the most powerful technologies for treating refractory organic wastewater. The Fenton technology has the characteristics of wide application range and mild reaction conditions, and provides a cheap and efficient source for hydroxyl radicals; on the other hand, the Fenton oxidation system utilizes an environment-friendly oxidant, namely hydrogen peroxide, and the final reaction product is water and carbon dioxide, so that the Fenton oxidation system also conforms to the concept of 'green chemistry'. However, the reaction needs to be carried out under severe acidic conditions, and a large amount of iron-containing sludge is generated in the process, thereby possibly causing a secondary pollution problem.
The development of a solid Fenton-like catalyst with high catalytic activity under a neutral condition is a main way for solving the defects of the traditional Fenton technology. The graphene material has rich specific surface area, and can improve the Fenton reaction rate by dispersing active components, improving the mass transfer rate and strengthening the electron transfer. Meanwhile, the material can also generate pi-pi interaction with aromatic rings, so that the enrichment of pollutants on the surface of a solid phase can be realized, and the degradation of the pollutants is accelerated. But the current graphene is high in price, and the direct use of the material for treating wastewater has no practical significance. Some natural polypeptides are reportedSugar materials such as chitosan and the like can produce similar graphene structures at high temperatures. Wherein, the chitosan has wide source and low price, and the molecular structure contains a large amount of-NH2and-OH groups, which can effectively bind metal ions by coordination. Therefore, the preparation cost of the graphitized carbon supported Fenton-like catalyst by using the material as a precursor can be expected to be reduced.
On the other hand, the separation and reuse performance is also an important factor limiting the use of the powder catalyst. By constructing the magnetic response characteristic, the material can keep smaller size, ensure the mass transfer rate and catalytic activity, and simultaneously contribute to the rapid separation and recovery of the material, thereby effectively reducing the use cost. In the existing reports, the magnetic particles and the functional material are compounded together by a dip-calcination method, a coating method, an in-situ precipitation method and the like. By a proper method, the magnetic Fenton-like catalyst is constructed, so that the treatment process can be further simplified, and the application of the technology in treating the refractory organic wastewater is promoted.
Disclosure of Invention
In order to solve the problems in the prior art, based on the analysis, the invention provides a preparation method of a magnetic multi-component iron-carbon composite Fenton-like catalyst, which is simple to operate and easy to realize industrialization.
The invention also provides the magnetic multi-component iron-carbon composite Fenton-like catalyst prepared by the preparation method, and the catalyst has higher Fenton-like catalytic activity under a neutral condition and can realize rapid separation through a magnetic field.
The invention also provides an application of the magnetic multi-component iron-carbon composite Fenton-like catalyst in catalytic oxidation degradation of organic pollutants.
A preparation method of a magnetic multi-component iron-carbon composite Fenton-like catalyst comprises the following steps:
(1) adding a carbon source into a ferrous sulfate aqueous solution, stirring and drying to obtain a precursor;
(2) and calcining the precursor, and then carrying out acid washing and activation to obtain the magnetic multi-component iron-carbon composite catalyst.
In the preparation method, the carbon source can be selected from long-chain polysaccharide rich in amino and hydroxyl, a three-dimensional network structure is formed after ferrous complexation and sulfate radical crosslinking, the carbon source is gradually converted into merle and pyrite and other components loaded by graphite carbon under the condition of oxygen isolation, and after inert components on the surface are removed, the Fenton-like catalyst with high reaction activity and magnetism is formed. The complexation of a carbon source in the precursor can form a 'confinement effect' on Fe atoms, and the formation of more nano-particles is promoted by reducing the contact among the Fe atoms during calcination, so that the dispersibility and the catalytic activity of the Fe are improved, the redox atmosphere around the Fe atoms during calcination is influenced, and the chemical state of the Fe is finally changed; and the graphene-like structure formed after the carbon source is carbonized can accelerate electron transfer, and the degradation of pollutants on the surface of the catalyst is realized through enhanced adsorption, so that the reaction can resist the interference of other components in the system.
In the above preparation method, in step (1):
preferably, the aqueous solution of ferrous sulfate is prepared by dissolving ferrous sulfate in water.
In order to prevent ferrous oxidation during the preparation process, preferably, nitrogen is introduced into water to remove oxygen in the water before the preparation process, the preparation process is kept sealed, and vacuum drying is adopted after the preparation process is finished.
The time for introducing nitrogen before preparation is preferably 1-60 min. More preferably 20 to 40 min.
Preferably, the carbon source is one or more of chitosan and cellulose.
Chitosan is also called deacetylated chitin, and is prepared from chitin widely existing in nature through deacetylation, and different deacetylation degrees determine the number of amino groups in molecules. Cellulose has the same carbon skeleton structure, but has no amino group in its molecule as compared with chitosan.
As a further preference, the carbon source is chitosan (degree of deacetylation 91.2% or 69.3%).
As a further preferable mode, the carbon source is chitosan having a deacetylation degree of 91.2% with abundant amino groups.
Preferably, the ratio of the amount of the ferrous sulfate substance to the mass of the carbon source in the aqueous solution is 2 to 6 mmol/g. More preferably 4.5 to 5.5 mmol/L.
Preferably, the stirring time is 2-5 h. In the stirring process, besides the complex reaction of polysaccharide and ferrous iron, in a chitosan system, due to the protonation of amino, the cross-linking reaction of sulfate radicals to different molecular chains can also occur. Thus, sufficient reaction time can ensure the formation of a three-dimensional network precursor. Wherein, magnetic stirring can be adopted for stirring.
More preferably, the stirring time is 3.5 to 4.5 hours.
In the above preparation method, in the step (2):
preferably, the precursor is calcined under the protection of nitrogen. Specifically, the precursor is placed in a tube furnace and calcined under the protection of nitrogen.
Preferably, the calcination temperature of the precursor is 800-1000 ℃, and the heating rate is 3-10 ℃/min; the calcination time is 3-5 h. When the calcining temperature is too low, the carbon is difficult to graphitize and the sulfate radical is difficult to reduce; when the calcination temperature is too high, the original graphitized carbon collapses to destroy the graphene structure.
More preferably, the calcination temperature is 900 ℃ and the temperature rise rate is 5 ℃/min; the calcination time was 4 h.
In order to prevent the powder from being scattered by the gas flow during the calcination, the precursor is preferably placed in a crucible with a lid and placed in a tube furnace for calcination.
Preferably, the calcined powder is acid-washed and activated with dilute sulfuric acid. The surface of the calcined iron component is easily coated by carbon, more active sites can be exposed by acid washing, the reaction activity is improved, and unstable iron components and impurities are removed.
Preferably, the concentration of the dilute sulfuric acid is 0.5 to 25 mmol/L.
Because the concentration of the sulfuric acid is too high, the effective iron component in the catalyst is lost, and the magnetism of the catalyst is weakened. More preferably 1 to 10 mmol/L. Still more preferably 2.5 mmol/L.
Preferably, the pickling and activating time is 0.5-24 h, and the temperature is 25-80 ℃.
The activation time can be greatly reduced by increasing the temperature, and further preferably, the pickling activation time is 1.5h, and the activation temperature is 80 ℃.
Preferably, after the completion of the acid washing activation, the activated powder sample is washed to be neutral by water and dried to obtain the magnetic multicomponent iron-carbon composite fenton-like catalyst.
The magnetic multi-component iron-carbon composite Fenton-like catalyst prepared by the preparation method has good Fenton-like catalytic performance, the removal efficiency of 50mg/L of acid red dye in 1 hour under a neutral condition reaches 99.9%, and after the reaction is finished, rapid solid-liquid separation can be realized by an external magnetic field, and the magnetic multi-component iron-carbon composite Fenton-like catalyst has good use stability. The principle is that through coordination complexation of ferrous chitosan and crosslinking action of sulfate radicals, components such as highly dispersed nano iron oxide, ferrous sulfide and the like are formed after calcination and activation, and the components have more active sites; fe (II) and Fe (III) exist on the surface of the catalyst at the same time, and in the presence of a graphene structure, the Fe (II) and the Fe (III) can realize rapid circulation and continuously catalyze hydrogen peroxide to generate hydroxyl radicals; meanwhile, the iron component and the carbon carrier are combined through a C-S-Fe stable bond, so that the stability of the material is ensured.
Specifically, the preparation method of the magnetic multi-component iron-carbon composite Fenton-like catalyst comprises the following steps:
(1) dissolving ferrous sulfate in water, adding a carbon source, stirring, drying to remove water to obtain a precursor, and calcining under the protection of nitrogen;
(2) and (3) placing the calcined powder into dilute sulfuric acid for activation, washing the calcined powder to be neutral, and drying the powder to obtain the magnetic multi-component iron-carbon composite Fenton-like catalyst.
A magnetic multi-component iron-carbon composite Fenton-like catalyst is prepared by any one of the preparation methods. The magnetic multi-component iron-carbon composite Fenton-like catalyst is applied to catalytic oxidation degradation of organic pollutants, and is simple to operate, high in degradation rate and stable in performance. The application of the magnetic multi-component iron-carbon composite Fenton-like catalyst in Fenton-like catalytic oxidation degradation of organic pollutants in wastewater.
When the magnetic multi-component iron-carbon composite Fenton-like catalyst is used for catalytic oxidation degradation of organic matters, the magnetic multi-component iron-carbon composite Fenton-like catalyst is directly put into wastewater to be treated (wastewater to be treated), and hydrogen peroxide is added. And the pollutant removal rate is high, the pH application range is wide, the operation is very simple, and the method has great practical value. Preferably, the organic pollutant is one or more of acid red dye and p-chlorophenol.
As a further preference, the organic contaminant is acid red 73(AR73) dye or p-chlorophenol.
In the catalytic oxidation degradation process, in the wastewater to be treated:
the addition amount of the hydrogen peroxide is preferably 10-50 mmol/L. Further preferably 40 mmol/L.
The addition amount of the magnetic multi-component iron-carbon composite Fenton-like catalyst is preferably 0.5-2 g/L. More preferably 1 to 2 g/L. Still more preferably 1.5 g/L.
The concentration of the organic pollutants is preferably 10-100 mg/L. More preferably 10 to 50 mg/L. More preferably 50 mg/L.
The pH value of the wastewater to be treated is preferably 2-9. When the pH value is less than 4, the iron seepage amount is more, which is not beneficial to the stable use of the catalyst; when the pH exceeds 8, the hydroxyl radical gradually combines with hydrogen peroxide to form O2The progress of the reaction is suppressed. Therefore, the pH value of the wastewater is more preferably 4 to 8.
In order to ensure that the magnetic multi-component iron-carbon composite Fenton-like catalyst is uniformly dispersed in a reaction system, the reaction is oscillated by a constant-temperature oscillation box in the reaction process, and solid-liquid separation is realized by an external magnetic field after the reaction is finished.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the magnetic multi-component iron-carbon composite Fenton-like catalyst is simple to operate and easy to realize industrialization. The magnetic multi-component iron-carbon composite Fenton-like catalyst prepared by the preparation method is high in catalytic activity, can effectively improve the pollutant degradation rate and is stable in performance when being applied to the process of degrading organic pollutants through catalytic oxidation, can be quickly separated through an external magnetic field, and is simple to operate, low in cost, wide in pH application range and high in practical value.
Drawings
In fig. 1:
(a) scanning electron microscope images of C-900 in comparative example 2 under different magnifications respectively;
(c) scanning electron microscope images of Fe/C-800 in example 1 under different magnifications respectively;
(e) scanning electron microscope images of Fe/C-900 of example 2 under different magnifications respectively;
(g) scanning electron microscope images of Fe/C-1000 in example 3 under different magnifications respectively;
(i) (j) are respectively scanning electron microscope images of Fe/Ce-900 in example 4 under different magnifications;
FIG. 2 is a Raman spectrum of Fe/C-800, Fe/C-900, Fe/C-1000, Fe/Ce-900 in examples 1-4;
FIG. 3 is an X-ray diffraction pattern (XRD) of Fe/C-800, Fe/C-900, Fe/C-1000, Fe/Ce-900 in examples 1-4;
FIG. 4 is a comparison of the fine structure spectrum of the L-edge X-ray of Fe in Fe/C-800, Fe/C-900, Fe/C-1000, Fe/Ce-900 of examples 1-4 with that of the iron standard sample;
FIG. 5 shows the addition of H to Fe/C-800, Fe/C-900, Fe/C-1000, Fe/Ce-900 in examples 1 to 42O2Catalytic degradation curve of dye AR73 in time, and no addition of H2O2The adsorption removal curve of the dye AR73 by Fe/C-900 in example 2;
in fig. 6:
(a) the hysteresis loop of Fe/C-900 in example 2;
(b) after degradation, carrying out solid-liquid separation by a magnet; in the figure, the separated catalyst Fe/C-900 is marked by a circle;
FIG. 7 is the paramagnetic resonance spectrum of Fe/C-900 with lutidine N-oxide (DMPO) as the trapping agent in example 2, wherein:
(a) is DMPO-O in a methanol system2 -A map;
(b) the spectrum of DMPO-HO & in the water system.
Detailed Description
The invention will now be further illustrated with reference to the following examples:
the raw materials used in the examples:
chitosan (deacetylation degree 91.2%) was purchased from zhejiang gold shell biochemistry ltd (yuhuan, zhejiang);
ferrous sulfate heptahydrate (analytically pure) was purchased from the national pharmaceutical group chemical agents limited (shanghai, china);
the water used for the experiment is ultrapure water (the resistance is more than or equal to 18.2M omega cm)-1)。
Examples 1 to 3
100mL of ultrapure water was charged into a 250mL beaker, nitrogen was bubbled for 30min to remove oxygen, and then 5.56g of FeSO was added4·7H2And O, slowly adding 4g of chitosan after dissolution, sealing with a sealing film, and keeping continuously stirring for 4 hours. And (3) performing rotary evaporation on the stirred mixed system, removing most of water, and continuously drying for 8 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the iron-carbon precursor. Putting the precursor into a corundum crucible with a cover, and performing nitrogen protection in a tube furnace at 5 ℃ for min-1The temperature rising rate of (2) was raised to a predetermined temperature (800 ℃, 900 ℃, 1000 ℃) in Table 1 and held for 4 hours.
Adding the calcined powder sample into enough 2.5mmol/L dilute sulfuric acid, activating at 80 ℃ for 1.5 hours, carrying out magnet separation, washing with water for multiple times until the solution is neutral, and drying to obtain the magnetic multi-component iron-carbon composite Fenton-like catalyst which is respectively marked as Fe/C-800, Fe/C-900 and Fe/C-1000.
TABLE 1 calcination temperature for each of the samples in examples 1-3
| Examples | Expression of the examples | Calcination temperature (. degree.C.) |
| 1 | Fe/C-800 | 800 |
| 2 | Fe/C-900 | 900 |
| 3 | Fe/C-1000 | 1000 |
Example 4
100mL of ultrapure water was charged into a 250mL beaker, nitrogen was bubbled for 30min to remove oxygen, and then 5.56g of FeSO was added4·7H2And O, after dissolving, slowly adding 4g of cellulose, sealing by a sealing film, and keeping continuously stirring for 4 hours. And (3) performing rotary evaporation on the stirred mixed system, removing most of water, and continuously drying for 8 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the iron-carbon precursor. Putting the precursor into a corundum crucible with a cover, and performing nitrogen protection in a tube furnace at 5 ℃ for min-1The temperature rise rate of (2) was increased to 900 ℃ and maintained for 4 hours.
And adding the calcined powder sample into enough 2.5mmol/L dilute sulfuric acid, activating at 80 ℃ for 1.5 hours, carrying out magnet separation, washing with water for multiple times until the solution is neutral, and drying to obtain the magnetic multi-component iron-carbon composite Fenton-like catalyst, wherein the concentration is recorded as Fe/Ce-900.
Comparative example 1
Putting chitosan into a corundum crucible with a cover, and performing nitrogen protection in a tube furnace at 5 ℃ for min-1The temperature rise rate of the reaction kettle is increased to 900 ℃ and kept for 4 hours,is marked as C-900.
Characterization of the catalyst 1
The scanning electron micrographs in FIG. 1 show the surface morphology of examples 1-4 and comparative example 1. As can be seen from (a) and (b) of fig. 1, the pure chitosan of comparative example 1 has a smooth surface of a fine block material after high-temperature calcination; after the ferrous sulfate is added (examples 1-3), the calcined materials in fig. 1 (c) - (h) are loose and porous. Fig. 1 (i) and (j) show that cellulose as the carbon precursor (example 4) still retains a fibrous morphology after calcination, and the particles are loosely bound to the fibers, indicating that the cellulose has a weak binding capacity to iron, resulting in poor binding of the iron component formed after calcination to carbon.
Specific surface areas and pore volumes of examples 1-4 and comparative example 1 are shown in Table 2, and the specific surface area of pure chitosan in comparative example 1 after calcination reaches 624.494m2(ii)/g, but the pore volume was only 0.080cc/g, indicating that micropores were found therein; in examples 1 to 4, the specific surface area was 47.4 to 87.7m2The pore volume is between 0.151 and 0.191cc/g, and the specific surface area is reduced compared with that of comparative example 2 due to the introduction of the iron component with higher density, but the pore structure is developed.
According to the literature, polysaccharide is gradually carbonized under high-temperature and anaerobic conditions, and the conversion from amorphous carbon to graphitized carbon is performed along with the increase of temperature, so that the transfer of electrons and the adsorption of pollutants are facilitated. However, as the temperature increases, the specific surface area and the pore volume tend to increase and then decrease (see table 2), because the carbonization degree is increased and the original channel structure is partially collapsed when the temperature is increased to 1000 ℃, and thus the specific surface area and the pore volume are maximized at 900 ℃.
TABLE 2 comparison of specific surface area and pore volume for examples 1-4 and comparative example 1
FIG. 2 shows the Raman spectra of the catalysts prepared in examples 1-4, wherein 1340cm-1The peak at (A) is a D band and represents a disordered sp3Vibration of hybrid carbon, 1591cm-1The peak at (A) is a G band representing an ordered sp2Vibration of hybrid carbon, strength ratio ID/IGCan reflect the graphitization degree of carbon in the material. As can be seen from FIG. 2, I's for Fe/C-800, Fe/C-900, Fe/C-1000 and Fe/Ce-900D/IGRespectively 0.91, 0.86, 0.89 and 1.01, which shows that the degree of carbon graphitization is highest at 900 ℃ by taking chitosan as a carbon precursor.
Characterization of the catalyst 2
The iron component of examples 1-4 was first characterized by XRD, with the results shown in FIG. 3. As can be seen in FIG. 3, the XRD peaks are substantially similar in the four catalysts, being characteristic faces of (100), (112), (114) and (300) of the merle FeS at 29.8 °, 33.6 °, 43.1 ° and 53.1 °, respectively, accompanied by pyrrhotite (Fe) at 43.6 °1-xS) characteristic crystal face, and hematite (alpha-Fe) at 35.5 DEG simultaneously2O3) Characteristic peak of (2).
While the fine structure spectrum of the iron L edge in FIG. 4 shows that the iron of the catalyst outer layer is closer to Fe2O3Rather than FeS in the bulk phase. It is concluded that, during high-temperature calcination, the reducing atmosphere of CO, C, etc. formed by carbonization of chitosan reduces sulfate and generates a series of iron sulfides with iron, and in the subsequent acid washing activation process, the FeS on the surface is oxidized under acidic and heating conditions and is converted into Fe in the subsequent water washing and drying process2O3. Thus surface Fe2O3Possibly the active site of the reaction, but alpha-Fe2O3The introduction of iron sulfide, especially strong-ferromagnetism pyrrhotite, increases the magnetic separation performance of the catalyst, and simultaneously increases the content of Fe (II) on the surface, thereby being beneficial to the Fe (III)/Fe (II) circulation process in Fenton-like reaction.
In the Fe/Ce-900 of example 4, in addition to the three iron-removing crystal forms, a small amount of iron simple substance exists, and FeSO is generated in the surface calcination process4The combination effect with cellulose is weaker, so that the cellulose is carbonized violently, the reducibility of the generated atmosphere is stronger, and the iron reduction is more violent.
Testing of catalyst Performance
Catalyst performance testing experiments were conducted in 250mL Erlenmeyer flasks, with a defined amount of the prepared catalyst sample and hydrogen peroxide solution (H)2 O 230%) into a 100mL solution containing acid red 73 dye (50mg/L by mass/volume), sealing the flask, placing the flask in a constant temperature vibration box, and oscillating the reaction at 25 ℃ and 150 rpm. Unless otherwise stated, the AR73 (acid Red 73) solution was pH-adjusted, the catalyst sample was added in an amount of 0.15g, the hydrogen peroxide was added in an amount of 0.4mL, and the catalytic degradation time was 1 hour. After the sample was taken out and filtered through a 0.45 μm filter, the absorbance was immediately measured at 508nm with an ultraviolet-visible spectrophotometer, and the remaining concentration of the dye was calculated.
Performance test example 1
Since acid Red 73(AR73) is a widely used azo dye that is difficult to degrade, it was considered in this study to be treated with the catalyst sample of example 2(Fe/C-900) and to use different amounts of catalyst and different amounts of H2O2Effect of dose on AR73 removal rate. Table 3 shows the effect of different catalyst amounts on acid Red 73 removal, as indicated by the results in H2O2When the adding amount is 50mmol/L, the removal rate of AR73 is gradually increased along with the increase of the using amount of Fe/C-900, but when the using amount is 1.5g/L, the removal rate reaches 99.2 percent, the use amount is continuously increased, the removal effect is not greatly changed, and therefore 1.5g/L is selected as the optimal adding amount of the catalyst.
TABLE 3 removal of AR73 for different catalyst loadings
| Catalyst dosage (g/L) | Removal Rate (%) |
| 0.5 | 33.8 |
| 1.0 | 82.0 |
| 1.5 | 99.2 |
| 2.0 | 100 |
| 2.5 | 100 |
Performance test example 2
Example 2(Fe/C-900) was selected as a sample of catalyst and H was examined at the optimum catalyst level selected above2O2The effect of AR73 removal rate (see table 4). Table 4 shows that H2O2When the adding amount is 20-50 mmol/L, the removal rate of AR73 is higher than 98%, and the removal rate of AR73 shows a trend of increasing first and then slightly decreasing, and when the adding amount is 40mmol/L, the removal rate of AR73 reaches the highest and is 99.85%. Due to excess H2O2Will react with the hydroxyl radical formed and therefore, when H is present2O2When the addition amount is increased to 50mmol/L, the removal rate is reduced. From this, the amount of catalyst added was determined to be 1.5g/L, H2O2The machine feeding amount is 40mmol/L, which is the best processing condition.
TABLE 4 different H2O2Removal rate of AR73 at dose
Performance test example 3
In order to verify the fenton-like catalytic performance of each catalyst sample, samples were taken at intervals (sampling intervals of 0, 5, 10, 15, 20, 30, 40, 50 and 60min) in the catalytic degradation experiments of AR73 in examples 1-4. As shown in FIG. 5, in the case of addition of H2O2In the case of (1), the removal of AR73 in example 2(Fe/C-900) reaches 97.8% in 20min, but the chroma remains at this time, and the removal rate of AR73 reaches 99.9% after 60min, and the chroma is basically removed. As a comparison, the removal rates at 60min for example 1(Fe/C-800, example 3(Fe/C-1000) and example 4(Fe/Ce-900) were 95.1%, 57.9% and 91.3%, respectively, thereby verifying that Fe/C-900 had the best removal effect on AR732O2The catalyst showed only adsorption, as can be seen from FIG. 5, Fe/C-900 (without addition of oxidant H)2O2) The adsorption removal rate at 60min for AR73 was 63.1%, indicating that in the above system, AR73 was the result of the combined action of adsorption and catalysis by the adsorbent.
In FIG. 6, (a) is the hysteresis loop of example 2(Fe/C-900), and (b) is a photograph of solid-liquid separation by a magnet after completion of degradation. Since the saturation magnetization of Fe/C-900 reached 5.08emu/g (see (a) in FIG. 6), as shown in (b) in FIG. 6, when an external magnetic field was applied, rapid solid-liquid separation could be achieved; the remanent magnetization was only 0.84emu/g, indicating that the catalyst powder was again dispersed in water when the external magnetic field was removed.
Performance test example 4
To verify the stability of the catalyst in use, the AR73 catalytic degradation experiment was performed once for example 2(Fe/C-900), the supernatant was removed by magnetic separation, the catalyst was dispersed again in 100mL of 50mg/L AR73 solution, and the catalytic degradation experiment was performed under the above-described optimum reaction conditions for 12 cycles in total, the results of which are shown in Table 5. As can be seen from Table 5, the Fe/C-900 stabilization performance is excellent, and the removal rate of AR73 in the 12 th cycle can be maintained at 92.26%, which is only 7.74% lower than the initial removal rate.
Table 5 removal of AR73 during recycle in example 3
| Number of cycles | Removal Rate (%) |
| 1 | 100 |
| 2 | 100 |
| 3 | 99.97 |
| 4 | 99.88 |
| 5 | 99.70 |
| 6 | 99.08 |
| 7 | 99.25 |
| 8 | 99.85 |
| 9 | 99.66 |
| 10 | 98.81 |
| 11 | 97.64 |
| 12 | 92.26 |
Performance test example 5
Since pH is an important factor affecting the effect of fenton reaction, the removal of AR73 was examined at different pH (2-9) (the pH of 50mg/L AR73 solution was about 6.8) in this study, and the results are shown in table 6. As can be seen from table 6, the removal rate of AR73 was extremely high under acidic and neutral conditions, indicating that the catalyst had good catalytic performance and was able to participate in the reaction normally. When the pH value is more than 7, the removal rate of AR73 is gradually reduced along with the increase of the pH value, and the activity is reduced; at pH 8, AR73 still had a 95.9% removal rate; and when the pH was 9, the removal rate of AR73 decreased to 85%. Table 6 also shows the leaching of Fe from the solution after the reaction at a corresponding pH value, and when the pH value is less than or equal to 3, the leaching rate of Fe is more than 2mg/L, which indicates that the catalyst can not maintain good stability under the pH condition. When the pH is 4 or more, the amount of iron eluted is small, and particularly, it is 0.399mg/L under neutral conditions (pH 7). Therefore, the pH of Fe/C-900 is preferably 4 to 8 in consideration of both the removal rate of AR73 and the amount of iron oozing.
TABLE 6 removal rate of AR73 and iron bleed amount under different pH conditions
Performance test example 6
In order to explore the reaction mechanism, dimethyl pyridine N-oxide (DMPO) is used as a trapping agent, and a paramagnetic resonance method is adopted to measure free radicals in the reaction. FIG. 7 (a) shows DMPO-O in a methanol system2 -FourThe doublet (b) in FIG. 7 is the quadruplet of DMPO-HO. in the aqueous system. FIG. 7 shows that Fe/C-900 catalyzes H2O2Production of HO and O2 -For degradation of contaminants.
Combining the above characterization and performance testing analysis, the reaction mechanism can be summarized as: Fe/C-900 attracts organic contaminants to the catalyst surface using graphitized carbon, while hydrogen peroxide decomposes on the iron component to produce HO & O, with the cycling of Fe (II) and Fe (III)2 -By means of the surface adsorption-degradation mode, HO in the system can be prevented-And the like, so that the pollutants can be efficiently removed under neutral and alkalescent conditions.
Claims (10)
1. A preparation method of a magnetic multi-component iron-carbon composite Fenton-like catalyst is characterized by comprising the following steps of:
(1) adding a carbon source into a ferrous sulfate aqueous solution, stirring and drying to obtain a precursor;
(2) and calcining the precursor, and then carrying out acid washing and activation to obtain the magnetic multi-component iron-carbon composite catalyst.
2. The preparation method of the magnetic multi-component iron-carbon composite Fenton-like catalyst according to claim 1, wherein the carbon source is one or more of chitosan and cellulose.
3. The method for preparing a magnetic multi-component iron-carbon composite Fenton-like catalyst according to claim 1, wherein in the step (1), the ratio of the amount of ferrous sulfate in the aqueous solution to the mass of the carbon source is 2 to 6 mmol/g.
4. The preparation method of the magnetic multi-component iron-carbon composite Fenton-like catalyst according to claim 1, wherein the precursor is calcined under the protection of nitrogen;
wherein the calcining temperature is 800-1000 ℃, and the heating rate is 3-10 ℃/min; the calcination time is 3-5 h.
5. The method for preparing a magnetic multicomponent iron-carbon composite Fenton-like catalyst according to claim 1, wherein in the step (2), the calcined powder is subjected to acid washing activation by using dilute sulfuric acid;
wherein the concentration of the dilute sulfuric acid is 0.5-25 mmol/L.
6. The preparation method of the magnetic multi-component iron-carbon composite Fenton-like catalyst according to claim 1, wherein the acid washing activation time is 0.5-24 hours and the temperature is 25-80 ℃.
7. A magnetic multi-component iron-carbon composite Fenton-like catalyst, which is prepared by the preparation method of any one of claims 1 to 6.
8. The application of the magnetic multi-component iron-carbon composite Fenton-like catalyst according to claim 7 in Fenton-like catalytic oxidative degradation of organic pollutants in wastewater.
9. The use according to claim 8, wherein the organic contaminant is one or more of an acid red dye, p-chlorophenol.
10. The application of the method as claimed in claim 8, wherein in the catalytic oxidation degradation process, the addition amount of hydrogen peroxide in the wastewater to be treated is 10-50 mmol/L; the addition amount of the magnetic multi-component iron-carbon composite Fenton-like catalyst is 0.5-2 g/L; the concentration of the organic pollutants is 10-100 mg/L; the pH value of the wastewater is 2-9.
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