CN114054027A - Graphite material modified red mud Fenton catalyst with magnetic separation performance and preparation method and application thereof - Google Patents
Graphite material modified red mud Fenton catalyst with magnetic separation performance and preparation method and application thereof Download PDFInfo
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- CN114054027A CN114054027A CN202111496680.7A CN202111496680A CN114054027A CN 114054027 A CN114054027 A CN 114054027A CN 202111496680 A CN202111496680 A CN 202111496680A CN 114054027 A CN114054027 A CN 114054027A
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- red mud
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- 239000007770 graphite material Substances 0.000 title claims abstract description 42
- 238000007885 magnetic separation Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006731 degradation reaction Methods 0.000 claims abstract description 39
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- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 9
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a graphite material modified red mud Fenton catalyst with magnetic separation performance and a preparation method and application thereof, and relates to the technical field of sewage treatment. The method specifically comprises the following steps: the red mud is subjected to acid treatment, carbon-containing reducing organic molecules and graphite oxide materials are impregnated and loaded on the surface of the red mud subjected to acid treatment and are dried, the magnetism of iron species contained in the red mud is regulated and controlled through the thermal reduction effect of decomposed substances under the inert calcination condition, and meanwhile, the graphite oxide materials are deoxidized and converted into high-conductivity graphite materials in the heat treatment process, so that the graphite material modified red mud heterogeneous catalyst loaded by the two-dimensional graphite materials and having the magnetic separation performance is obtained. The catalyst prepared by the invention can be used for Fenton-like catalytic degradation of pollutants in wastewater, realizes a magnetic separation effect by means of the magnetism of iron-containing oxides in red mud after the degradation reaction is finished, does not generate secondary pollution, and has a wide application prospect in wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a graphite material modified red mud Fenton catalyst with magnetic separation performance, and a preparation method and application thereof.
Background
The Fenton-like technology is a novel advanced oxidation water treatment technology, and becomes a research hotspot due to the characteristics of high reaction efficiency, thorough reaction, no secondary pollution and the like. In recent years, researchers have synthesized a variety of heterogeneous catalysts for use with H2O2A Fenton-like reaction system is constructed, particularly, oxides represented by iron-containing compounds can catalyze and decompose hydrogen peroxide to generate OH for degrading organic pollutants, and the defects that a homogeneous Fenton system is low in required pH value and narrow in application range, and a large amount of sludge is generated due to the existence of iron ions in the reaction process are overcome. Nevertheless, these catalyst synthesis often need comparatively loaded down with trivial experimental steps, inevitably bring the reduction of catalytic activity again in the catalyst shaping process, and the effect of removing the pollutant is still poor. Therefore, on the basis of ensuring the surface active sites of the catalyst, the solid-liquid separation effect under the assistance of the magnetic particles in a liquid phase system is introduced, and a new idea is hopefully provided for the development of the high-efficiency Fenton-like catalyst.
China is the biggest world alumina production country, and the produced alumina accounts for more than half of the total amount of the whole world. In the production process of alumina, every 1t of alumina is produced, about 1.0-1.8 t of red mud solid waste residue is discharged. The red mud contains a large amount of strong alkaline substances, and high-alkalinity sewage permeates underground or enters surface water to cause serious pollution to surface water and underground water. In addition, a great deal of piling up of the red mud causes great waste of land resources, and how to accelerate the comprehensive utilization of the red mud becomes a great problem at present. In fact, the main component of red mud is Al2O3、Fe2O3、SiO2And TiO2These are also precisely the basic constituents of many fenton-like catalysts. E.g. by passing through appropriate red bloodThe mud modification method fully activates the Fenton-like active sites on the surface of the red mud, simultaneously exerts the advantages of the iron-containing oxides in the red mud, develops the red mud Fenton-like catalyst with magnetic separation performance, and undoubtedly has important research value.
According to the reports, roasting magnetization can be used for regulating and controlling the magnetic performance of red mud, and the patent 'method for reducing iron oxide in red mud by biomass and synchronously improving the activity of inorganic components' (publication number: CN107311479B) discloses a method for reducing iron oxide in red mud by using biomass as a reducing agent, and the patent 'preparation method of red mud-carbon-based magnetic composite material' (publication number: CN105801077A) discloses a method for generating a magnetic red mud composite material by reducing methanol in high-temperature reaction. It is not easy to find that the carbon material formed by carbonizing and cracking the carbon-containing substances is mainly amorphous structure and mostly irregular blocky product, and it is difficult to form an efficient charge transfer interface between the carbon material and the iron oxide for generating pollutants in water by radical oxidation. Therefore, how to fully utilize the red mud and the graphite materials and prepare the fenton-like reaction catalyst by a simple and efficient method is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a graphite material modified red mud Fenton catalyst with magnetic separation performance, which is used for modifying red mud industrial solid waste based on a heterogeneous catalysis interface charge regulation and control principle.
In order to achieve the purpose, the invention provides a preparation method of a graphite material modified red mud Fenton catalyst with magnetic separation performance, which specifically comprises the following steps:
1) putting the red mud into an acid solution, stirring, centrifuging, washing and drying solid water, and dispersing a dried product into deionized water to obtain a red mud suspension;
2) adding carbon-containing organic molecules and graphite oxide materials into the red mud suspension, uniformly stirring, washing with centrifugal water, and drying solids to obtain a red mud mixed catalyst;
3) calcining the red mud mixed catalyst at high temperature in an inert atmosphere, and cooling to obtain the graphite material modified red mud Fenton catalyst with magnetic separation performance.
In a preferred embodiment, in the step 1), the red mud is raw red mud powder, and the content of iron oxide in the red mud is 5% or more.
In the invention, the red mud is not required to be pretreated, and the original red mud material with the ferric oxide content of more than 5 percent is directly utilized, so that the problems of land occupation and serious pollution caused by industrial solid waste accumulation are solved.
In a preferred embodiment, in step 1), the acidic solution is an inorganic acid solution with a concentration of 0.1-5M, and the inorganic acid solution comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; more preferably, the concentration of the mineral acid is 3M.
The source of inorganic acid is rich, the cost is low, and the alkali metal and the alkaline earth metal in the red mud can be removed by treating the red mud with the acid solution, so that a proper acid environment is provided for Fenton-like reaction.
In a preferred embodiment, in the step 1), the solid-to-liquid ratio of the red mud to the acidic solution is 1: (1-20) (g/ml);
the concrete operation of stirring is: stirring at 25-60 deg.C for 1-12h, preferably 2-6h at 25 deg.C; the specific operation of drying is as follows: drying at 60-80 deg.C for 6-12h, preferably at 80 deg.C for 12 h.
In a preferred embodiment, in step 1), the solid-to-liquid ratio of the oven-dried product to the deionized water is 1: (80-120) (g/ml).
In a preferred embodiment, in the step 2), the carbon-containing organic molecule comprises one or more of urea, melamine, glucose, chitosan, starch, oxalic acid and citric acid; in the process of high-temperature carbonization, carbon-containing organic molecules can form a protective layer on the surface of the red mud to prevent excessive iron ions from being separated out, and can be used as a reducing agent to reduce ferric oxide in the red mud into ferroferric oxide, so that the prepared catalyst has magnetism; and simultaneously, in the process of selecting the carbon-containing organic molecules, the cost economy and the reduction functionality of raw materials are considered, so the carbon-containing organic molecules are selected, and more preferably, the carbon-containing organic molecules are melamine, oxalic acid and citric acid.
The graphite oxide material comprises one or more of self-prepared or commercially available graphene, graphene oxide and graphite powder, and the thickness of the graphite oxide material can be a single-layer or multi-layer structure. The graphite oxide material has a layered structure, so that the surface area of the catalyst can be increased, and more active sites are provided for subsequent reactions; meanwhile, the graphite oxide material can be used as a good conductor of electrons, so that the transmission of photo-generated electrons is accelerated in the photo-Fenton reaction process, and the Fe content is further improved2+And Fe3+Finally, the degradation rate of the pollutants is improved.
In a preferred embodiment, in the step 2), the weight ratio of the red mud, the carbon-containing organic molecules and the graphite oxide material is 1 (0.3-3) to (0.005-0.1). In the experimental process, a series of catalysts are prepared by carrying out experiments with different proportions, and then pollutant degradation performance tests are carried out, so that the optimal mass ratio is obtained after optimization. In the experimental process, a very thick carbon layer coating is formed when the carbon-containing organic molecules are excessive, which is not beneficial to the Fenton reaction; if the carbon-containing organic molecules are too few, too much iron ions are separated out, and secondary pollution is caused. If the amount of the graphite oxide materials is too much, the catalytic reaction is not affected, and the preparation cost of the catalyst is increased; too little will not utilize the transmission of photo-generated electrons, thereby affecting the degradation properties of the contaminants. Therefore, the raw material weight ratio is limited to the above range.
In a preferred embodiment, in the step 2), the specific operation of stirring is: stirring for 1-6h at room temperature, preferably for 2-4 h; the specific operation of drying is as follows: drying at 60-80 deg.C for 6-12h, preferably at 60 deg.C for 10 h.
In a preferred embodiment, in the step 3), the inert gas includes nitrogen or argon; the high-temperature calcination conditions are as follows: heating to 400-900 ℃ at the temperature rising rate of 5 ℃ per minute, and carrying out high-temperature calcination for 0.5-8 hours.
The invention also aims to provide the graphite material modified red mud Fenton catalyst with the magnetic separation performance, the magnetic performance of the red mud solid waste is regulated and controlled through the in-situ pyrolysis reduction of carbon-containing organic molecules, meanwhile, a reaction interface for efficient charge separation and transfer is constructed by using a two-dimensional graphite material formed by thermal reduction, and the activity of the Fenton-like reaction catalyst is improved by means of the strong interface action between the red mud and the two-dimensional graphite material.
The invention also aims to provide an application of the graphite material modified red mud-based Fenton catalyst with the magnetic separation performance in the field of wastewater treatment, the modified Fenton catalyst with high catalytic efficiency is combined with light source irradiation, the degradation effect on pollutants in a water body is further improved, and after degradation is finished, the catalyst is adsorbed out by using an external magnetic field by using the magnetic performance of the modified Fenton catalyst and is reused.
The application specifically comprises the following steps: mixing the modified red mud Fenton catalyst, an organic pollutant aqueous solution and an oxidant, reacting under the irradiation of a light source to promote the degradation of pollutants, and adsorbing the catalyst in the aqueous solution by using an external magnetic field after the degradation is finished.
In a preferred embodiment, the organic contaminants include dye molecules, antibiotics, fluorine-containing compounds, endocrine disruptors, soluble organic matter in the actual wastewater.
In a preferred embodiment, the oxidizing agent comprises one of hydrogen peroxide, peroxymonosulfate, peroxydisulfate; the dosage of the hydrogen peroxide oxidant is 0.01-0.5M; the dosage of the peroxymonosulfate or peroxydisulfate oxidant is 0.1-3M; the dosage of the modified red mud Fenton catalyst is 0.2-5 g/L.
In a preferred embodiment, the light source comprises a simulated xenon lamp, a high-pressure ultraviolet lamp, actual sunlight and the like, and the intensity of the light source is 100-300mW/cm2;
Photo-generated electrons generated by the modified red mud Fenton catalyst under light excitation are quickly transferred to the surface of the conductive graphite material and then converted into active oxygen radicals, and the active oxygen radicals and pollutants adsorbed on the surface of the graphite material are subjected to redox reaction, so that the degradation effect is enhanced;
in the preparation process of the modified red mud Fenton catalyst, the magnetic separation performance of the red mud powder is endowed by virtue of cracking and carbonizing of organic molecules, the red mud powder can be gathered and separated from a water body under the action of an external magnetic field, and the collected catalyst can be recycled.
Compared with the prior art, the graphite material modified red mud Fenton catalyst with the magnetic separation performance and the preparation method and the application thereof have the following advantages:
1. in the invention, waste red mud industrial waste is selected as a raw material, so that the cost is low, the yield is rich, and the resource waste caused by the accumulation of a large amount of red mud as industrial solid waste in the prior art can be solved.
2. According to the invention, the magnetic performance and the charge transfer capacity of the catalyst are regulated and controlled through a simple acid treatment, carbon material compounding and high-temperature atmosphere calcination mode, a new magnetic separation function is endowed to red mud powder by virtue of cracking and carbonization of organic molecules, meanwhile, a more ideal reaction interface is provided for efficient transfer of catalyst interface charges by utilizing a two-dimensional graphite material generated by thermal reduction, oxidants such as hydrogen peroxide and persulfate are efficiently activated, active oxygen radicals are generated to degrade pollutants in water, and a new method is provided for safe and green removal of pollutants in water while resource utilization of red mud is realized.
3. The prepared sex red mud Fenton catalyst has good effect of degrading water pollutants, can generate degradation effect on various pollutants, has good universality, is convenient to recover after degradation, and still has good degradation capability after repeated use.
4. The preparation method is simple, the raw materials are wide in source, the cost is low, the raw materials are easy to collect and obtain, and the preparation method is particularly suitable for large-scale industrial production and preparation.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a TEM image of a graphite-based material modified red mud-based Fenton catalyst with magnetic separation performance prepared in example 1;
FIG. 2 is a graph showing the performance effect of the graphite material modified red mud Fenton catalyst in application example 1 in cooperation with a hydrogen peroxide on degrading rhodamine B under dark conditions, wherein C/C in ordinate0Representing the ratio of the concentration of rhodamine B at the time t to the initial concentration;
FIG. 3 is a graph showing the performance effect of the graphite material modified red mud Fenton catalyst in application example 2 on degradation of rhodamine B under the synergistic effect of the hydrogen peroxide illumination condition, wherein C/C in the ordinate0Representing the ratio of the concentration of rhodamine B at the time t to the initial concentration;
fig. 4 is a magnetic separation performance verification of the graphite material-modified red mud-based fenton catalyst in application example 1.
Detailed Description
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by an existing method, and the room temperature in the present invention is 25 ℃.
Example 1
Selecting red mud with ferric oxide content of more than 5% as a reaction raw material, adding the red mud into 50mL of hydrochloric acid (1M) solution, wherein the solid-to-liquid ratio of the red mud to the hydrochloric acid is 1:10(g/mL), and stirring and reacting for 12 hours at room temperature;
washing the red mud subjected to acid treatment with water centrifugally for 5 times, drying the red mud at 80 ℃ for 12 hours, weighing 1g of the red mud, dispersing the red mud in 100ml of deionized water to obtain a suspension, respectively adding urea and graphene oxide to the suspension, wherein the graphene oxide is a single-layer sample, the mass ratio of the red mud to the urea is 1:1, the mass ratio of the red mud to the graphene oxide is 1:0.02, stirring the mixture at room temperature for 6 hours, separating and drying the mixture to obtain a powder sample;
heating a sample with the surface impregnated and loaded with urea and graphene oxide to 550 ℃ at a heating rate of 5 ℃ per minute in a nitrogen atmosphere, and calcining at high temperature for 4 hours to generate a graphite material modified red mud catalyst with magnetic separation performance;
the morphology of the prepared modified red mud Fenton catalyst is shown in figure 1, and the close contact between the iron oxide particles and the two-dimensional graphite material sheet layer can be seen from the figure, so that the high-efficiency activation and free radical generation by interface charge transfer are facilitated.
Example 2
Selecting red mud with ferric oxide content of more than 5% as a reaction raw material, adding the red mud into 50mL of sulfuric acid (1M) solution, wherein the solid-to-liquid ratio of the red mud to the sulfuric acid is 1:10(g/mL), and stirring and reacting for 12 hours at room temperature;
washing the red mud subjected to acid treatment with water centrifugally for 5 times, drying the red mud at 80 ℃ for 12 hours, weighing 1g of the red mud, dispersing the red mud in 100ml of deionized water to obtain a suspension, respectively adding urea and graphene oxide to the suspension, wherein the graphene oxide is a single-layer sample, the mass ratio of the red mud to the urea is 1:1, the mass ratio of the red mud to the graphene oxide is 1:0.02, stirring the mixture at room temperature for 6 hours, separating and drying the mixture to obtain a powder sample;
and (3) heating the sample with the surface impregnated and loaded with urea and graphene oxide to 550 ℃ at the heating rate of 5 ℃ per minute in the nitrogen atmosphere, and calcining at high temperature for 4 hours to generate the graphite material modified red mud catalyst with the magnetic separation performance.
Example 3
Selecting red mud with ferric oxide content of more than 5% as a reaction raw material, adding the red mud into 50mL of hydrochloric acid (1M) solution, wherein the solid-to-liquid ratio of the red mud to the hydrochloric acid is 1:10(g/mL), and stirring and reacting for 12 hours under the heating condition of 60 ℃;
washing the red mud subjected to acid treatment with water centrifugally for 5 times, drying the red mud at 80 ℃ for 12 hours, weighing 1g of the red mud, dispersing the red mud in 100ml of deionized water to obtain a suspension, respectively adding urea and graphene oxide to the suspension, wherein the graphene oxide is a single-layer sample, the mass ratio of the red mud to the urea is 1:1, the mass ratio of the red mud to the graphene oxide is 1:0.02, stirring the mixture at room temperature for 6 hours, separating and drying the mixture to obtain a powder sample;
and (3) heating the sample with the surface impregnated and loaded with urea and graphene oxide to 550 ℃ at the heating rate of 5 ℃ per minute in the nitrogen atmosphere, and calcining at high temperature for 4 hours to generate the graphite material modified red mud catalyst with the magnetic separation performance.
Example 4
Selecting red mud with ferric oxide content of more than 5% as a reaction raw material, adding the red mud into 50mL of hydrochloric acid (1M) solution, wherein the solid-to-liquid ratio of the red mud to the hydrochloric acid is 1:10(g/mL), and stirring and reacting for 12 hours at room temperature;
washing the red mud subjected to acid treatment with water for 5 times in a centrifugal mode, drying the red mud for 12 hours at the temperature of 80 ℃, weighing 1g of the red mud, dispersing the red mud in 100ml of deionized water to obtain a suspension, adding oxalic acid and graphene oxide into the suspension respectively, wherein the graphene oxide is a single-layer sample, the mass ratio of the red mud to the oxalic acid is 1:1, the mass ratio of the red mud to the graphene oxide is 1:0.02, stirring the mixture for 6 hours at room temperature, separating and drying the mixture to obtain a powder sample;
and (3) heating the sample with the surface impregnated and loaded with the oxalic acid and the graphene oxide to 550 ℃ at the heating rate of 5 ℃ per minute in the nitrogen atmosphere, and calcining at high temperature for 4 hours to generate the graphite material modified red mud catalyst with the magnetic separation performance.
Example 5
Selecting red mud with ferric oxide content of more than 5% as a reaction raw material, adding the red mud into 50mL of hydrochloric acid (1M) solution, wherein the solid-to-liquid ratio of the red mud to the hydrochloric acid is 1:10(g/mL), and stirring and reacting for 12 hours at room temperature;
washing the red mud subjected to acid treatment with water for 5 times in a centrifugal mode, drying the red mud at the temperature of 80 ℃ for 12 hours, weighing 1g of the red mud, dispersing the red mud in 100ml of deionized water to obtain a suspension, adding glucose and graphene oxide into the suspension respectively, stirring the mixture at room temperature for 6 hours, separating and drying the mixture to obtain a powder sample, wherein the graphene oxide is a single-layer sample, the mass ratio of the red mud to the glucose is 1:1, and the mass ratio of the red mud to the graphene oxide is 1: 0.02;
and (3) heating the sample with the surface impregnated and loaded with glucose and graphene oxide to 550 ℃ at the heating rate of 5 ℃ per minute in the nitrogen atmosphere, and calcining at high temperature for 4 hours to generate the graphite material modified red mud catalyst with the magnetic separation performance.
Example 6
Selecting red mud with ferric oxide content of more than 5% as a reaction raw material, adding the red mud into 50mL of hydrochloric acid (1M) solution, wherein the solid-to-liquid ratio of the red mud to the hydrochloric acid is 1:10(g/mL), and stirring and reacting for 12 hours at room temperature;
washing the red mud subjected to acid treatment with water for 5 times in a centrifugal mode, drying the red mud for 12 hours at the temperature of 80 ℃, weighing 1g of the red mud, dispersing the red mud in 100ml of deionized water to obtain a suspension, adding melamine and graphene oxide into the suspension respectively, wherein the graphene oxide is a single-layer sample, the mass ratio of the red mud to the melamine is 1:1, the mass ratio of the red mud to the graphene oxide is 1:0.02, stirring the mixture for 6 hours at room temperature, separating and drying the mixture to obtain a powder sample;
and (3) heating the sample with the surface impregnated and loaded with melamine and graphene oxide to 550 ℃ at the heating rate of 5 ℃ per minute in the nitrogen atmosphere, and calcining at high temperature for 4 hours to generate the graphite material modified red mud catalyst with the magnetic separation performance.
Example 7
Selecting red mud with ferric oxide content of more than 5% as a reaction raw material, adding the red mud into 50mL of hydrochloric acid (1M) solution, wherein the solid-to-liquid ratio of the red mud to the hydrochloric acid is 1:10(g/mL), and stirring and reacting for 12 hours at room temperature;
washing the red mud subjected to acid treatment with water for 5 times in a centrifugal mode, drying the red mud at the temperature of 80 ℃ for 12 hours, weighing 1g of the red mud, dispersing the red mud in 100ml of deionized water to obtain a suspension, adding citric acid and graphene oxide into the suspension respectively, stirring the mixture at room temperature for 6 hours, separating and drying the mixture to obtain a powder sample, wherein the graphene oxide is a single-layer sample, the mass ratio of the red mud to the citric acid is 1:1, and the mass ratio of the red mud to the graphene oxide is 1: 0.02;
and (3) heating the sample with the surface impregnated and loaded with citric acid and graphene oxide to 550 ℃ at the heating rate of 5 ℃ per minute in the nitrogen atmosphere, and calcining at high temperature for 4 hours to generate the graphite material modified red mud catalyst with the magnetic separation performance.
Application example 1
The invention provides an application of a graphite material modified red mud Fenton catalyst in catalytic water purification, which comprises the following steps:
the modified red mud-based Fenton catalyst prepared in the example 5 is added into 100ml of rhodamine B dye solution, the mixture is stirred for 2 hours at room temperature under the dark condition, a certain amount of hydrogen peroxide is added after adsorption-desorption equilibrium is achieved, Fenton-like reaction under the dark condition is started, the graphite material can efficiently capture free electrons in molecular orbits of iron compounds in the red mud and transfer the free electrons to the hydrogen peroxide, and then the free electrons are activated to generate strong oxidizing hydroxyl radicals for degrading pollutants. The concentration of rhodamine B is selected to be 20mg/L, the adding amount of the Fenton-like catalyst is 1g/L, and the using amount of the hydrogen peroxide oxidant is 0.05M;
after a certain time interval, filtering a certain volume of reaction solution by using a microfiltration membrane with the aperture of 0.45 micrometer to obtain a test sample solution, measuring the concentration ℃ of the residual dye in the solution by using a spectrophotometric temperature method, and calculating the removal rate of pollutants; the results are shown in FIG. 2.
As can be seen from the figure, the original red mud almost has no degradation effect on rhodamine B, the sample which is only subjected to acid treatment and is not modified by glucose and graphene oxide has the degradation rate of 18.5% on rhodamine B within 90min, and the degradation rate of the sample of the red mud modified by glucose and graphene oxide on rhodamine B within 90min can reach 98.4%.
After the reaction, the solid-liquid separation of the red mud catalyst powder was carried out by the magnet, and as shown in fig. 4, it was found that the separation and extraction of the red mud powder could be favorably carried out by the action of the applied magnetic field. The collected catalyst can also be directly used for subsequent pollutant degradation reaction, and the degradation rate can still reach more than 96% after the catalyst is recycled for 6 times.
Application example 2
The modified red mud Fenton catalyst prepared in the example 5 is added into 100ml of rhodamine B dye solution, stirred for 2 hours at room temperature under the dark condition, a certain amount of hydrogen peroxide is added after adsorption-desorption equilibrium is achieved, and a xenon lamp is turned onThe simulated light source provides conditions for the photo-Fenton reaction, the photo-excited red mud catalyst generates more photo-generated electrons and is captured by the high-conductivity two-dimensional graphite material, and free electrons are transferred to hydrogen peroxide to be further activated to generate strong-oxidizing hydroxyl radicals for degrading pollutants. The concentration of rhodamine B is selected to be 20mg/L, the dosage of Fenton-like catalyst is 1g/L, the dosage of hydrogen peroxide oxidant is 0.05M, and the xenon lamp light source intensity is 200mW/cm2;
After a certain time interval, filtering a certain volume of reaction solution by using a microfiltration membrane with the aperture of 0.45 micrometer to obtain a test sample solution, measuring the concentration ℃ of the residual dye in the solution by using a spectrophotometric temperature method, and calculating the removal rate of pollutants; the results are shown in FIG. 3.
As can be seen from the figure, the original red mud/H2O2The degradation rate of the photoproduction system to rhodamine B in 20min is 49.9 percent; glucose and graphene oxide modified red mud/H2O2The degradation rate of the system to rhodamine B within 20min is 78.8 percent; the degradation rate of the glucose and graphene oxide modified red mud/luminophor system on rhodamine B within 20min is 20.1%; glucose and graphene oxide modified red mud/H2O2The degradation rate of the photoperiod system to rhodamine B within 20min is 99.8 percent. Compared with the previous application example, the application example 1 is a pure Fenton reaction, the application example 2 is a photo-Fenton reaction, and the difference is that after light is introduced into the application example 2, the photocatalysis and the Fenton reaction are performed in a synergistic manner, so that the degradation effect is greatly improved, and the degradation capability of the graphite material modified red mud-based Fenton catalyst on water pollutants is further improved.
After the reaction is finished, the magnet is utilized to carry out solid-liquid separation on the red mud catalyst powder, the collected catalyst is directly used for subsequent pollutant degradation reaction, and the degradation rate can still reach more than 95% after the catalyst is recycled for 6 times.
Application example 3
Adding a certain amount of modified red mud Fenton catalyst into methylene blue dye solution, stirring for 2 hours at room temperature under dark condition, adding a certain amount of peroxodisulfate after reaching adsorption-desorption balance, starting xenonThe lamp simulation light source provides conditions for light Fenton reaction, the red mud catalyst excited by light generates more photo-generated electrons and is captured by the high-conductivity two-dimensional graphite material, and free electrons are transferred to persulfate to further activate to generate strong-oxidizing sulfate radicals and hydroxyl radicals for degrading pollutants. The concentration of methylene blue is 20mg/L, the dosage of Fenton-like catalyst is 1g/L, the dosage of persulfate oxidant is 0.35M, and the intensity of xenon lamp light source is 200mW/cm2;
After a certain time interval, filtering a certain volume of reaction solution by using a microfiltration membrane with the aperture of 0.45 micrometer to obtain a test sample solution, measuring the concentration ℃ of the residual dye in the solution by using a spectrophotometric temperature method, and calculating the removal rate of pollutants; the degradation data for methylene blue within 10min for this application example, corresponding to examples 1-7, are shown in Table 1:
TABLE 1 degradation effect of different graphite materials modified red mud Fenton catalysts on methylene blue within 10min
Graphite material modified red mud Fenton catalyst | Rate of degradation |
Example 1 | 97.1% |
Example 2 | 94.6% |
Example 3 | 99.5% |
Example 4 | 97.6% |
Example 5 | 99.8% |
Example 6 | 98.7% |
Example 7 | 89.6% |
After the reaction is finished, the magnet is utilized to carry out solid-liquid separation on the red mud catalyst powder, the collected catalyst is directly used for the subsequent pollutant degradation reaction, and after the catalyst of the embodiments 1 to 7 is recycled for 6 times, the degradation rate is not more than 2% different from that of the catalyst used for the first time.
Application example 4
Adding a certain amount of graphite material modified red mud Fenton catalyst into a bisphenol A solution, stirring for 2 hours at room temperature and in the dark, adding a certain amount of peroxydisulfate after reaching adsorption-desorption balance, starting a xenon lamp simulation light source to provide conditions for light Fenton reaction, generating more photo-generated electrons by the photo-excited red mud catalyst and capturing the photo-generated electrons by a high-conductivity two-dimensional graphite material, and transferring free electrons to persulfate to further activate to generate strong-oxidative sulfate radicals and hydroxyl radicals for degrading pollutants. Selecting 10mg/L of bisphenol A at the concentration ℃, adding 1g/L of Fenton-like catalyst, using 0.35M of persulfate oxidant and 200mW/cm of xenon lamp light source at the strong temperature2;
After a certain time interval, filtering a certain volume of reaction solution by using a microfiltration membrane with the pore diameter of 0.45 micrometer to obtain a test sample solution, measuring the concentration ℃ of the residual bisphenol A in the solution by using high performance liquid chromatography, and calculating the removal rate of pollutants; the degradation data for bisphenol A in 15min for this application example, corresponding to examples 1-7, are shown in Table 2:
table 2 degradation effect of different graphite materials modified red mud Fenton catalysts on bisphenol A within 15min
Graphite material modified red mud Fenton catalyst | Rate of degradation |
Example 1 | 92.3% |
Example 2 | 93.7% |
Example 3 | 96.8% |
Example 4 | 95.2% |
Example 5 | 97.9% |
Example 6 | 91.7% |
Example 7 | 88.3% |
After the reaction is finished, the magnet is utilized to carry out solid-liquid separation on the red mud catalyst powder, the collected catalyst is directly used for the subsequent pollutant degradation reaction, and after the catalyst of the embodiments 1 to 7 is recycled for 6 times, the degradation rate is not more than 1.8% different from that of the catalyst used for the first time.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A preparation method of a graphite material modified red mud Fenton catalyst with magnetic separation performance is characterized by comprising the following steps:
1) putting the red mud into an acid solution, stirring, centrifuging, washing and drying solid water, and dispersing a dried product into deionized water to obtain a red mud suspension;
2) adding carbon-containing organic molecules and graphite oxide materials into the red mud suspension, uniformly stirring, washing with centrifugal water, and drying solids to obtain a red mud mixed catalyst;
3) calcining the red mud mixed catalyst at high temperature in an inert atmosphere, and cooling to obtain the graphite material modified red mud Fenton catalyst with magnetic separation performance.
2. The method according to claim 1, wherein in the step 1), the acidic solution is an inorganic acid solution having a concentration of 0.1 to 5M;
the solid-to-liquid ratio of the red mud to the acidic solution is 1: (1-20) (g/ml);
the concrete operation of stirring is: stirring for 1-12h at 25-60 deg.C;
the specific operation of drying is as follows: drying at 60-80 deg.C for 6-12 h.
3. The preparation method of claim 1, wherein in the step 1), the solid-to-liquid ratio of the dried product to the deionized water is 1: (80-120) (g/ml).
4. The method of claim 1, wherein in step 2), the carbon-containing organic molecule comprises one or more of urea, melamine, glucose, chitosan, starch, oxalic acid and citric acid;
the graphite oxide material comprises one or more of graphene, graphene oxide and graphite powder.
5. The preparation method of claim 1, wherein in the step 2), the weight ratio of the red mud, the carbon-containing organic molecules and the graphite oxide material is 1 (0.3-3) to (0.005-0.1);
the concrete operation of stirring is: stirring for 1-6h at room temperature;
the specific operation of drying is as follows: drying at 60-80 deg.C for 6-12 h.
6. The method according to claim 1, wherein in the step 3), the inert gas comprises nitrogen or argon; the high-temperature calcination conditions are as follows: heating to 400-900 ℃ at the temperature rising rate of 5 ℃ per minute, and carrying out high-temperature calcination for 0.5-8 hours.
7. The graphite-based material modified red mud-based Fenton catalyst with magnetic separation performance prepared by the preparation method of any one of claims 1 to 6.
8. Use of the modified red mud-based fenton catalyst of claim 7 in wastewater treatment.
9. The use according to claim 8, comprising in particular the steps of: mixing the modified red mud Fenton catalyst, an organic pollutant aqueous solution and an oxidant, reacting under the irradiation of a light source to promote the degradation of pollutants, and adsorbing the catalyst in the aqueous solution by using an external magnetic field after the degradation is finished.
10. The use of claim 9, wherein the oxidizing agent comprises one of hydrogen peroxide, peroxymonosulfate, peroxydisulfate; the dosage of the hydrogen peroxide oxidant is 0.01-0.5M; the dosage of the peroxymonosulfate or peroxydisulfate oxidant is 0.1-3M;
the dosage of the modified red mud Fenton catalyst is 0.2-5 g/L.
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