CN115582125B - Composite material for catalyzing advanced oxidation of ozone, preparation method and application - Google Patents
Composite material for catalyzing advanced oxidation of ozone, preparation method and application Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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- 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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Abstract
The application relates to a composite material for catalyzing advanced oxidation of ozone, a preparation method and application thereof, and belongs to the technical field of ozone catalysis. Comprising the following steps: cleaning the surface, and removing oxides on the surface to obtain pretreated iron shavings; carrying out surface modification on the pretreated iron shavings by adopting a surface electrolysis treatment method; putting the iron shavings into a polyvinyl alcohol solution with a molecular weight of 120,000 ～ 150,000, taking out, airing to be semi-dry, putting the iron shavings into the polyvinyl alcohol solution for 2-3 minutes, and taking out for later use; sprinkling modified activated carbon particles on the surfaces of the iron shavings and gaps inside the iron shavings so that the modified activated carbon particles are uniformly adhered to the iron shavings; filling into a mold, and pressing to form. The diameter of the pore canal can be adjusted as required, and the modified activated carbon is added to be pressed and shaped together, so that micropores are increased, the roughness of the micro-channels can be increased, the friction and collision between ozone and the catalyst during circulation are increased, and the catalytic effect is improved.
Description
Technical Field
The application relates to the technical field of ozone catalysis, in particular to a composite material for catalyzing advanced oxidation of ozone, a preparation method and application.
Background
The ozone catalysis technology is to enhance the oxidation performance of ozone and improve the utilization efficiency of ozone under the action of a catalyst, and can completely degrade or convert the organic components difficult to degrade in sewage in a short time by catalyzing the ozone oxidation reaction, thereby realizing the purpose of purifying the water body.
However, in the related art, microchannel integral masonry filler for catalyzing ozone to form advanced oxidation is used for ozone treatment of wastewater, and wood shavings or scrap iron are taken as raw materials to be placed in a die and mechanically compressed into a unit module. However, the filler has obvious defects that the catalytic material is single, the surface is a corrosion-resistant gamma-FeOOH compact layer, and the gamma-FeOOH catalytic ozone capacity is weaker than that of other metal oxides although the iron price is low; and the gamma-FeOOH surface cannot be modified, so that the catalytic capability of the gamma-FeOOH is limited.
There are also related arts: the filler of the activated carbon-loaded multi-metal oxide catalyzes ozone, the effect is good, but because the activated carbon particles have closed micropores and no channels, ozone gas is still insufficient to contact with the activated carbon particles when flowing, so that the activated carbon-loaded multi-metal oxide filler still has room for improvement in the process of catalyzing the application of ozone to advanced oxidation. The current method for improving the catalytic capability of the activated carbon supported oxide to ozone is to change the means including changing the type of the supported metal, changing the content of the supported metal, increasing or decreasing the specific surface area of the activated carbon, but the pore characteristics cannot be changed fundamentally.
Disclosure of Invention
In order to solve the problems and defects in the related art, the application tries to compound the iron shavings and the activated carbon into relatively uniform whole-masonry filler, which is generally considered to be difficult to realize in the technical field, because the iron shavings are loose, the activated carbon is granular, the two are simply mixed, the activated carbon is accumulated below, and the filler is obviously layered after being compacted. Therefore, the application overcomes the technical prejudice and successfully combines the iron shavings with the activated carbon to prepare the composite material for catalyzing the advanced oxidation of ozone.
In one aspect, the application provides a method for preparing a composite material for catalyzing advanced oxidation of ozone, comprising the steps of:
(1) Surface-treating the iron shavings:
cleaning the surface, and removing oxides on the surface to obtain pretreated iron shavings;
carrying out surface modification on the pretreated iron shavings by adopting a surface electrolysis treatment method;
soaking the iron shavings in a polyvinyl alcohol solution with a molecular weight of 120,000 ～ 150,000 for 2-3 min, taking out and airing to be semi-dry, and then placing the iron shavings in the polyvinyl alcohol solution for 2-3 min and taking out for later use;
(2) Sprinkling modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the iron shavings, so that the modified activated carbon particles are uniformly adhered to the iron shavings;
(3) Filling into a mold, and pressing to form.
Optionally, the surface modification of the pretreated iron shavings by adopting a surface electrolysis treatment method comprises the following steps:
placing the pretreated iron shavings in a metal cage, connecting the metal cage with a direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in an electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing and aging in the electrolyte, taking the metal cage out of the electrolyte, taking the iron shavings out of the metal cage, and naturally air-drying to finish surface modification.
Optionally, the voltage of the direct current power supply is 30V-45V.
Optionally, the mass ratio of the modified activated carbon to the iron shavings is 1 (30-100).
Optionally, the electrolyte is Na 2 CO 3 And NaHCO 3 Mixing the solution, wherein Na 2 CO 3 The concentration of (2) is 1-3 mol/L NaHCO 3 The concentration is 0.5-2 mol/L.
Optionally, the mass ratio of the modified activated carbon to the iron shavings is: 1 (30-100).
Optionally, the polyvinyl alcohol solution is prepared according to the mass ratio of polyvinyl alcohol to water of 1:5-20.
Optionally, the modified activated carbon particles are obtained by the following method:
immersing activated carbon in a mixed salt solution containing manganese chloride, cobalt chloride and copper chloride according to m Manganese chloride ：m Cobalt chloride ：m Copper chloride = (1 to 4): (2-3): (2-5) and the soaking time is 30-6Taking out the mixture for 0min, airing the mixture, isolating the mixture from air, calcining the mixture for 3 to 6h, and cooling the mixture to the room temperature.
In another aspect, the application provides a composite material for catalyzing advanced oxidation of ozone, prepared by any one of the preparation methods.
On the other hand, the application also provides application of the composite material for catalyzing the advanced oxidation of ozone, which is applied to wastewater treatment.
On the other hand, the application also provides application of any preparation method, which is applied to wastewater treatment.
The application has at least the following beneficial effects:
(1) Covering PVA on the surface of the compacted material, and washing to remove the PVA, wherein the PVA is used as a pore template agent to obtain a through pore on the surface of the iron wire; (2) The modified activated carbon particles are uniformly adhered to the gaps of the materials, and then the iron wires are compressed for deformation, so that a relatively uniform mixing effect can be obtained; (3) By mixing the iron wire with the activated carbon, micropores from the channels of the activated carbon and micro channels from the channels left after the PVA is removed can be obtained. (4) Through adjusting the thickness of PVA, wash again and get rid of, can be more convenient adjust the diameter of pore as required. (5) The activated carbon is added for pressing and shaping, so that micropores can be increased, the roughness of the micro-channels can be increased, and friction and collision between ozone and the catalyst during circulation are increased.
Detailed Description
The preparation method of the composite material for catalyzing the advanced oxidation of ozone in the specific embodiment of the application comprises the following steps:
(1) Firstly, the surface of the iron shavings or the fine iron wires is treated:
cleaning the surface, namely removing greasy dirt and other stains on the surface, oxides on the surface and the like, and obtaining pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings: in some embodiments of the application, the pretreated iron shavings are placed in a metal cage, the metal cage is connected with a direct current power supply anode, a power supply cathode is connected with a carbon rod, the metal cage and the carbon rod are placed in electrolyte, the distance between the metal cage and the carbon rod is 3 cm to 10cm, the power supply is switched on, the power supply is switched off after electrolysis for 10 minutes to 30 minutes, the metal cage is placed in the electrolyte for standing and aging, the metal cage is taken out of the electrolyte, and then the metal cage is taken out of the electrolyte, and the metal cage is naturally air-dried, so that the surface modification is completed;
soaking the iron shavings in a polyvinyl alcohol (PVA) solution with a molecular weight of 120,000 ～ 150,000, taking out, airing to be semi-dry, putting the iron shavings in the PVA solution for 2-3 minutes for standby; so far, in order to finish twice soaking, multiple soaking can be performed, different PVA covering layers can be obtained through the soaking times, and then the thickness of PVA on the surface of the iron shavings is controlled, the pore size is not required to be controlled through pressure, and the pressure cannot ensure that the upper control and the lower control of pressing are consistent, because the deformation after the upper, middle and lower stress is inconsistent during pressing. When PVA with the molecular weight of 120,000 ～ 150,000 is adhered to the surface of the iron shavings, the surface of the iron shavings is in an activated state due to the adsorption effect, the deformation of the iron shavings is easy to carry out, and the deformation is changed from elastic deformation to plastic deformation, so that the elastic aftereffect can be greatly reduced, and the porosity of the filler is increased.
The molecular weight of the polyvinyl alcohol is less than 120,000 or more than 150,000, the activation degree of the surface of the iron shavings is low, and the iron shavings are not easy to deform.
(2) Sprinkling modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the iron shavings, so that the modified activated carbon particles are uniformly adhered to the iron shavings; because PVA is introduced, the activated carbon particles are attached to the surfaces of the iron shavings and then pressed, so that the iron shavings and the activated carbon can be uniformly pressed together. The filler loaded in the activated carbon can fully exert activity, and breaks through the limitation that only gamma-FeOOH acts originally.
(3) Filling into a mould, pressing, taking out the formed filler, soaking in water to fully dissolve PVA, taking out the filler, flushing with water, and airing to obtain the composite material. In some embodiments, to fully dissolve the PVA, hot water at 60-70℃is typically used for 24-36 hours. The density of the pressed filler is not needed to be considered during pressing, and PVA attached to the outer surface of the iron shavings is dissolved after the pressed filler is soaked in hot water, so that the position of a pore channel is reserved. The filler in the embodiment of the present application refers to the iron shavings obtained in the step (2) that have been adhered with the modified activated carbon particles.
The wall of the micro-channel formed by dissolving PVA is iron shavings and modified active carbon, the active carbon can increase the roughness of the micro-channel, and water flow and air flow can fully contact with the active carbon when flowing through the micro-channel.
The specific embodiment of the application relates to a preparation method of a composite material for catalyzing advanced oxidation of ozone, and the voltage of a direct current power supply is 30-45V. The voltage is lower than 30V, so that the efficiency is low; the voltage is higher than 45V, the cost is high, and the benefit is low.
The application relates to a preparation method of a composite material for catalyzing ozone advanced oxidation, wherein the electrolyte is Na 2 CO 3 And NaHCO 3 Mixed solution of Na 2 CO 3 The concentration of (2) is 1-3 mol/L NaHCO 3 The concentration is 0.5-2 mol/L. By way of illustration, in the mixed solution, na 2 CO 3 The concentration of (C) may be 1mol/L,2mol/L,3mol/L, etc., naHCO 3 The concentration is 0.5mol/L,1mol/L,2mol/L, etc.
The preparation method of the composite material for catalyzing the advanced oxidation of ozone in the specific embodiment of the application comprises the following steps of: 1 (30-100). In the dosage range, the activated carbon can ensure that the pore canal between the scrap iron is kept smooth, and the material performance is not reduced due to escape in use.
The preparation method of the composite material for catalyzing the advanced oxidation of ozone in the specific embodiment of the application comprises the step of preparing a polyvinyl alcohol solution according to the mass ratio of polyvinyl alcohol to water of 1:5-20. By way of illustration, in some embodiments, the mass ratio of polyvinyl alcohol to water in the polyvinyl alcohol solution may be 1:5,1:6,1:7,1:8, & gt, 1:18,1:19,1:20, etc. When the mass ratio of the polyvinyl alcohol to the water is not in the above range, the reaction efficiency and the yield are low.
The preparation method of the composite material for catalyzing ozone advanced oxidation in the specific embodiment of the application comprises the following steps of:
immersing activated carbon into a mixed salt solution, wherein the mixed salt solution contains manganese chloride, cobalt chloride and copper chloride, and the mass ratio of the manganese chloride to the cobalt chloride is m Manganese chloride ：m Cobalt chloride ：m Copper chloride = (1 to 4): (2-3): and (2-5) in proportion, wherein the soaking time is 30-60 min, taking out, airing, isolating air, calcining for 3-6 h, and cooling to room temperature. In some embodiments, m Manganese chloride ：m Cobalt chloride ：m Copper chloride =1:2:4, 2:3:4;3:2.5:5,4:2:3, etc., the proportions of the three salts herein are not particularly limited as long as they are within the above-mentioned proportion ranges.
The composite material for catalyzing the advanced oxidation of ozone, which is provided by the specific embodiment of the application, is prepared by adopting any of the preparation methods.
The composite material for catalyzing advanced oxidation of ozone, which is provided by the embodiment of the application, is applied to wastewater treatment.
Likewise, the preparation method of the composite material for catalyzing the advanced oxidation of ozone, which is provided by the embodiment of the application, is applied to wastewater treatment.
The technical solution of the present application will be clearly and completely described in connection with the following embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort are within the scope of the present application based on the embodiments of the present application.
The modified activated carbon related to the embodiment of the application is obtained by the following methods:
immersing 1kg of active carbon sold in the market into 10L of mixed salt solution for 30-60 min, wherein the mixed salt solution contains 100-400 g of manganese chloride, 200-300 g of cobalt chloride and 200-500 g of copper chloride, taking out and airing, isolating air, calcining for 3-6 h, and cooling to room temperature to obtain the required modified active carbon.
EXAMPLE 1 preparation of composite Material I for catalyzing advanced ozone oxidation
(1) Firstly, the surface of the iron shavings or the fine iron wires is treated:
removing oil stains and other stains on the surface and oxides on the surface to obtain pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings:
placing pretreated iron shavings in a metal cage, connecting the metal cage with a 30V direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing in the electrolyte for 60 minutes, taking out the metal cage from the electrolyte, taking out the metal cage, and naturally airing to finish surface modification;
and then placing the iron shavings into a polyvinyl alcohol solution with the molecular weight of 120,000 for soaking for 2min, taking out and airing to be semi-dry, placing the iron shavings into the polyvinyl alcohol solution for 2-3 min, and taking out for standby, thus completing 2 times of soaking. (2) Scattering modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the surface of the iron shavings, wherein the mass ratio of the modified activated carbon to the iron shavings subjected to surface treatment is 1:30, so that the activated carbon particles are uniformly adhered to the iron shavings;
(3) Filling into a mold, pressing, taking out the formed filler, soaking in hot water at 60deg.C for 36 hr
And (3) fully dissolving PVA, taking out the filler, flushing with water, and airing to obtain the composite material I. Example 2 preparation of composite Material II for catalyzing advanced ozone oxidation
Firstly, the surface of the iron shavings or the fine iron wires is treated:
(1) Removing oil stains and other stains on the surface and oxides on the surface to obtain pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings:
placing pretreated iron shavings in a metal cage, connecting the metal cage with a 40V direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing in the electrolyte for 30 minutes, taking out the metal cage from the electrolyte, taking out the metal cage, and naturally airing to finish surface modification;
putting the iron shavings into a polyvinyl alcohol solution with the molecular weight of 130,000 for soaking for 3min, taking out and airing to be semi-dry, putting the iron shavings into the polyvinyl alcohol solution for 2-3 min, taking out for standby, and finishing 1-time soaking; repeating the soaking steps for 2 times to finish 2 times of soaking;
(2) Scattering modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the surface of the iron shavings, wherein the mass ratio of the modified activated carbon to the iron shavings subjected to surface treatment is 1:50, so that the activated carbon particles are uniformly adhered to the iron shavings;
(3) Filling into a mold, pressing, taking out the formed filler, soaking in hot water at 65deg.C for 30 hr
And (3) fully dissolving PVA, taking out the filler, washing with water, and airing to obtain the composite material II.
Example 3 preparation of composite III for catalytic ozone advanced oxidation
Firstly, the surface of the iron shavings or the fine iron wires is treated:
(1) Removing oil stains and other stains on the surface and oxides on the surface to obtain pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings:
placing pretreated iron shavings in a metal cage, connecting the metal cage with a 45V direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing in the electrolyte for 40 minutes, taking out the electrolyte from the metal cage, and naturally airing to finish surface modification;
putting the iron shavings into a polyvinyl alcohol solution with the molecular weight of 150,000 for soaking for 2min, taking out and airing to be semi-dry, putting the iron shavings into the polyvinyl alcohol solution for 2-3 min, taking out for standby, and finishing 1-time soaking; repeating the soaking steps for 3 times to finish 3 times of soaking;
(2) Scattering modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the surface of the iron shavings, wherein the mass ratio of the modified activated carbon to the iron shavings subjected to surface treatment is 1:100, so that the activated carbon particles are uniformly adhered to the iron shavings;
(3) Filling into a mould, pressing, taking out the formed filler, soaking in hot water at 70 ℃ for 24 hours to fully dissolve PVA, taking out the filler, flushing with water, and airing to obtain the composite material III.
Comparative example 1
Firstly, the surface of the iron shavings or the fine iron wires is treated:
(1) Removing oil stains and other stains on the surface and oxides on the surface to obtain pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings:
placing pretreated iron shavings in a metal cage, connecting the metal cage with a 50V direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing and ageing in the electrolyte for 20 minutes, taking out the electrolyte from the metal cage, and naturally airing to finish surface modification;
putting the iron shavings into a polyvinyl alcohol solution with the molecular weight of 180,000 for soaking for 3min, taking out and airing to be semi-dry, putting the iron shavings into the polyvinyl alcohol solution for 2-3 min, taking out for standby, and finishing 1-time soaking;
(2) Scattering modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the surface of the iron shavings, wherein the mass ratio of the modified activated carbon to the iron shavings subjected to surface treatment is 1:50, so that the activated carbon particles are uniformly adhered to the iron shavings;
(3) Filling into a mould, pressing, taking out the formed filler, soaking in hot water at 80 ℃ for 20 hours to fully dissolve PVA, taking out the filler, flushing with water, and airing to obtain the composite material A.
Comparative example 2
Firstly, the surface of the iron shavings or the fine iron wires is treated:
(1) Removing oil stains and other stains on the surface and oxides on the surface to obtain pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings:
placing pretreated iron shavings in a metal cage, connecting the metal cage with a 25V direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing and aging in the electrolyte for 70 minutes, taking out the electrolyte from the metal cage, and naturally airing to finish surface modification;
putting the iron shavings into a polyvinyl alcohol solution with the molecular weight of 110,000, soaking for 2min, taking out, airing to be semi-dry, putting the iron shavings into the polyvinyl alcohol solution for 2-3 min, taking out for standby, and finishing 1-time soaking;
(2) Scattering modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the surface of the iron shavings, wherein the mass ratio of the modified activated carbon to the iron shavings subjected to surface treatment is 1:30, so that the activated carbon particles are uniformly adhered to the iron shavings;
(3) Filling into a mould, pressing, taking out the formed filler, soaking in hot water at 80 ℃ for 20 hours to fully dissolve PVA, taking out the filler, flushing with water, and airing to obtain the composite material B.
Comparative example 3
Firstly, the surface of the iron shavings or the fine iron wires is treated:
(1) Removing oil stains and other stains on the surface and oxides on the surface to obtain pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings:
placing pretreated iron shavings in a metal cage, connecting the metal cage with a 30V direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing and aging in the electrolyte for 60 minutes, taking out the electrolyte from the metal cage, and naturally airing to finish surface modification;
(2) Scattering modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the surface of the iron shavings, wherein the mass ratio of the modified activated carbon to the iron shavings subjected to surface treatment is 1:20;
(3) Filling into a mould, pressing, taking out the formed filler, soaking in hot water at 60 ℃ for 36 hours, taking out the filler, flushing with water, and airing to obtain the composite material C.
Comparative example 4
Firstly, the surface of the iron shavings or the fine iron wires is treated:
(1) Removing oil stains and other stains on the surface and oxides on the surface to obtain pretreated iron shavings;
and then adopting a surface electrolysis treatment method to modify the surface of the pretreated iron shavings:
placing pretreated iron shavings in a metal cage, connecting the metal cage with a 30V direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after 10-30 minutes of electrolysis, standing and aging in the electrolyte for 60 minutes, taking out the electrolyte from the metal cage, and naturally airing to finish surface modification;
(2) Filling into a mould, pressing, taking out the formed filler, soaking in hot water at 60 ℃ for 36 hours, taking out the filler, flushing with water, and airing to obtain the composite material D.
EXAMPLE 4 comparison of the effects of various materials in treating wastewater
The general method is adopted: through testing, when the stacking height of the filler is 100cm and the flow rate of the wastewater to be treated is 0.5m/min, the pressure drop at the inlet end and the outlet end is shown in the following table, the ozone inlet amount is 25mg/L, and potassium dichromate is adoptedMethod (COD) Cr ) GB11914-89 tests show that the initial COD is 410-450 mg/L, and after one month of continuous operation, the COD removal rate is detected for 7 continuous days, and the average removal effect of the COD is compared with that of 7 continuous days, see the following table:
| type of material | COD removal rate | Pressure drop (cm water column) |
| Composite material I | 92.3％ | 8 |
| Composite material II | 93.5％ | 6 |
| Composite material III | 98.1％ | 5 |
| Composite A | 91.0％ | 8 |
| Composite material B | 91.5％ | 8 |
| Composite C | 89.5％ | 36 |
| Composite material D | 52.9％ | 43 |
The above-described preferred embodiments according to the present application are intended to suggest that, in view of the above description, various changes and modifications may be made by the worker in question without departing from the technical spirit of the present application. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of claims.
Claims (8)
1. A method for preparing a composite material for catalyzing advanced oxidation of ozone, which is characterized by comprising the following steps:
(1) Surface-treating the iron shavings:
cleaning the surface, and removing oxides on the surface to obtain pretreated iron shavings;
carrying out surface modification on the pretreated iron shavings by adopting a surface electrolysis treatment method;
putting the iron shavings into a polyvinyl alcohol solution with the molecular weight of 120,000-150,000, soaking, taking out, airing to be semi-dry, putting the iron shavings into the polyvinyl alcohol solution for 2-3 minutes, and taking out for later use;
(2) Sprinkling modified activated carbon particles on the surface of the iron shavings subjected to surface treatment and gaps inside the iron shavings, so that the modified activated carbon particles are uniformly adhered to the iron shavings;
(3) Filling into a mould, pressing and forming, taking out the formed filler, soaking in water to enable PVA to be fully dissolved, taking out the filler, flushing with water, and airing to obtain the composite material;
wherein the modified activated carbon particles are obtained by the following method:
immersing activated carbon into a mixed salt solution, wherein the mixed salt solution contains manganese chloride, cobalt chloride and copper chloride,according to mass ratio of m Manganese chloride ：m Cobalt chloride ：m Copper chloride = (1-4): (2-3): and (2-5) in proportion, wherein the soaking time is 30-60 min, taking out, airing, isolating air, calcining for 3-6 h, and cooling to room temperature.
2. The method for preparing a composite material for catalyzing advanced oxidation of ozone as set forth in claim 1, wherein the surface modification of the pretreated iron shavings by a surface electrolytic treatment method comprises the steps of:
placing the pretreated iron shavings in a metal cage, connecting the metal cage with a direct current power supply anode, connecting a power supply cathode with a carbon rod, placing the metal cage and the carbon rod in an electrolyte, separating the metal cage and the carbon rod by 3-10cm, switching on the power supply, switching off the power supply after electrolysis for 10-30 minutes, standing and aging in the electrolyte, taking the metal cage out of the electrolyte, taking the iron shavings out of the metal cage, and naturally air-drying to finish surface modification.
3. The method for preparing a composite material for catalyzing advanced oxidation of ozone as set forth in claim 2, wherein the voltage of the direct current power supply is 30v to 45v.
4. The method for preparing a composite material for catalyzing advanced oxidation of ozone as set forth in claim 3, wherein the electrolyte is Na 2 CO 3 And NaHCO 3 Mixed solution of Na 2 CO 3 The concentration of (2) is 1-3 mol/L NaHCO 3 The concentration is 0.5-2 mol/L.
5. The method for preparing a composite material for catalyzing advanced oxidation of ozone as set forth in claim 4, wherein the mass ratio of the modified activated carbon to the iron shavings is 1 (30-100).
6. The method for preparing a composite material for catalyzing advanced oxidation of ozone as set forth in claim 5, wherein the polyvinyl alcohol solution is prepared according to a mass ratio of polyvinyl alcohol to water of 1:5-20.
7. A composite material for catalyzing advanced oxidation of ozone, characterized in that it is prepared by the method of any one of claims 1 to 6.
8. Use of a composite material for catalyzing advanced oxidation of ozone according to claim 7, characterized by being applied to wastewater treatment.
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