CN113979516A - Iron-carbon-copper alloy micro-electrolysis composite material and preparation method and application thereof - Google Patents

Iron-carbon-copper alloy micro-electrolysis composite material and preparation method and application thereof Download PDF

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CN113979516A
CN113979516A CN202111342187.XA CN202111342187A CN113979516A CN 113979516 A CN113979516 A CN 113979516A CN 202111342187 A CN202111342187 A CN 202111342187A CN 113979516 A CN113979516 A CN 113979516A
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copper alloy
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孔令涛
谢超
刘锦淮
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Hefei Institutes of Physical Science of CAS
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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Abstract

The invention belongs to the technical field of wastewater treatment, and provides an iron-carbon-copper alloy micro-electrolysis composite material, wherein the preparation raw materials of the composite material comprise boron carbide, coal powder, iron powder, copper oxide powder, a pore-forming agent and water; the mass ratio of the boron carbide, the coal powder, the iron powder, the copper oxide powder and the pore-forming agent is 5-10: 10-20: 60-80: 5-10: 0.5-1.5; the mass volume ratio of the iron powder to the water is 0.6-0.8 kg: 100-150 mL. The invention also provides a preparation method and application of the iron-carbon-copper alloy micro-electrolysis composite material. The iron-carbon-copper alloy micro-electrolysis composite material has a compact structure, high hardness and remarkably improved strength and corrosion resistance; no adhesive is added, the effective components are high, the iron element proportion reaches more than 70 percent, and the precipitation amount of ineffective residues is obviously reduced.

Description

Iron-carbon-copper alloy micro-electrolysis composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an iron-carbon-copper alloy micro-electrolysis composite material and a preparation method and application thereof.
Background
The micro-electrolysis technology is a catalytic reduction water treatment technology, can realize the breakage of organic pollutant molecular chains, the change of chemical bonds and the transfer of energy inside a structure, can reduce the toxicity of organic pollutants, improve the biodegradability of wastewater and realize the strengthening treatment of refractory wastewater, and is widely applied to the treatment of industrial wastewater. In addition, the technology can be combined with hydrogen peroxide to form a micro-electrolysis-Fenton oxidation-flocculation precipitation process, and can effectively reduce indexes of various pollutants such as Chemical Oxygen Demand (COD), ammonia nitrogen, chromaticity, suspended matter concentration (SS) and the like. At present, a great deal of work is done on the preparation process of the micro-electrolysis composite material, the shape and the structure of the micro-electrolysis composite material are continuously improved by taking raw materials such as iron, carbon, clay and the like as main materials, and the preparation process is mainly characterized in that the carbon precursors are different, the clay is selected differently and the like. The prior art discloses that bamboo powder is used as a carbon precursor to be sintered to form porous carbon to prepare a micro-electrolysis composite material, although the cost is saved, the clay proportion of the material can reach 40%, the effective component of iron and carbon is low, the crushing strength is low, and the industrial application of the material is limited. The prior art also discloses a preparation method of the iron-based multi-metal alloy micro-electrolysis material, which adopts high-temperature sintering of various metals, but mainly depends on the action of clay and a binder during molding, and the proportion reaches more than 20 percent; in another example, graphite and alumina are used as catalysts to enhance the transfer of electrons in the interior of the micro-electrolysis material and accelerate the diffusion of an oxidation film. However, the catalyst needs to be fired separately, and the process is complex, so that the catalyst is difficult to be applied in the market in a large scale.
Therefore, the research and development of the micro-electrolysis composite material which has high hardness, high crushing strength, good stability, good corrosion resistance and good wastewater treatment effect, reduces the oxidation hardening and has simple preparation process has important value and significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an iron-carbon-copper alloy micro-electrolysis composite material, a preparation method and application thereof, which are used for solving the problems of low hardness, low strength, easy hardening, large clay mixing amount, low effective component and poor stability of a micro-electrolysis water material in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an iron-carbon-copper alloy micro-electrolysis composite material, which is prepared from the following raw materials of boron carbide, coal powder, iron powder, copper oxide powder, a pore-forming agent and water;
the mass ratio of the boron carbide, the coal powder, the iron powder, the copper oxide powder and the pore-forming agent is 5-10: 10-20: 60-80: 5-10: 0.5-1.5;
the mass volume ratio of the iron powder to the water is 0.6-0.8 kg: 100-150 mL.
Preferably, the preparation method of the boron carbide comprises the following steps: mixing carbon black and boric acid, and calcining to obtain boron carbide;
the calcining temperature is 1600-1700 ℃, and the time is 1-2 h; the calcination is carried out under the condition of isolating air;
the mass ratio of the carbon black to the boric acid is 50-60: 40-50; the particle size of the carbon black is 50-150 mu m.
Preferably, the particle diameters of the pulverized coal, the iron powder and the copper oxide powder are independently 50-150 μm.
Preferably, the pore-forming agent comprises oxalic acid and/or tartaric acid.
The invention also provides a preparation method of the iron-carbon-copper alloy micro-electrolysis composite material, which comprises the following steps:
1) mixing boron carbide, coal powder, iron powder, copper oxide powder, a pore-forming agent and water, and then pressing and forming to obtain a formed product;
2) and calcining and quenching the formed product in sequence to obtain the iron-carbon-copper alloy micro-electrolysis composite material.
Preferably, the mixing time in the step 1) is 0.5-2 h, and the pressure of the compression molding is 4-10 MPa.
Preferably, the calcining temperature in the step 2) is 1700-1900 ℃, and the time is 1-2 h; the calcination is carried out under exclusion of air.
Preferably, the quenching treatment time in the step 2) is 20-50 s; the medium for quenching treatment is water or sodium chloride solution.
Preferably, the mass concentration of the sodium chloride solution is 0.8-1.2%.
The invention also provides application of the iron-carbon-copper alloy micro-electrolysis composite material in wastewater treatment.
The beneficial effects of the invention include the following:
1) the boron carbide enables the iron-carbon-copper alloy micro-electrolysis composite material to have the characteristics of hardness, low expansion coefficient and the like based on the atomic clusters formed by the carbon-boron covalent bond action, so that the space structure stability, the hardness, the crushing strength, the chemical corrosion resistance and the plate bonding resistance of the composite material can be improved, and the mechanical stability of the composite material in the using process is improved; the potential difference of the material is changed, the diffusion of the composite material oxidation film is promoted, and the anti-hardening effect of the composite material is improved.
2) The copper oxide powder is ionized into ionic crystals at high temperature, and the microscopic crystal face angle can be changed after calcination, so that the electrochemical performance of the composite material is improved, and the corrosion resistance of the composite material is enhanced.
3) The iron-carbon-copper alloy micro-electrolysis composite material has a compact structure, high hardness and remarkably improved strength and corrosion resistance; no adhesive is added, the effective components are high, the iron element proportion reaches more than 70 percent, and the precipitation amount of ineffective residues is obviously reduced.
4) The iron-carbon-copper alloy micro-electrolysis composite material has high repeated utilization rate, has excellent performance in micro-electrolysis and Fenton-like reactions of various industrial wastewater such as printing and dyeing wastewater, electroplating wastewater, papermaking wastewater, pharmaceutical wastewater and the like, and can strengthen the treatment of the industrial wastewater.
Drawings
FIG. 1 is an SEM image of an iron-carbon-copper alloy microelectrolytic composite of example 1;
FIG. 2 is a topographical view of the iron-carbon-copper alloy microelectrolytic composite of example 1;
fig. 3 is an energy spectrum of the iron-carbon-copper alloy microelectrolytic composite of example 1.
Detailed Description
The invention provides an iron-carbon-copper alloy micro-electrolysis composite material, which is prepared from the following raw materials of boron carbide, coal powder, iron powder, copper oxide powder, a pore-forming agent and water;
the mass ratio of the boron carbide, the coal powder, the iron powder, the copper oxide powder and the pore-forming agent is 5-10: 10-20: 60-80: 5-10: 0.5-1.5;
the mass volume ratio of the iron powder to the water is 0.6-0.8 kg: 100-150 mL.
The mass ratio of the boron carbide, the coal powder, the iron powder, the copper oxide powder and the pore-forming agent is preferably 6-9: 12-18: 65-75: 6-9: 0.7-1.2, more preferably 7-8: 14-16: 67-72: 7-8: 0.8-1.1, and more preferably 7.5:15:70:7.5: 0.9-1.
The mass volume ratio of the iron powder to the water is preferably 0.65-0.75 kg: 110 to 140mL, more preferably 0.68 to 0.72 kg: 120-130 mL, more preferably 0.7 kg: 125 mL.
The preparation method of boron carbide of the present invention preferably comprises the steps of: mixing carbon black and boric acid, and calcining to obtain boron carbide;
the calcination temperature is preferably 1600-1700 ℃, more preferably 1620-1680 ℃, and more preferably 1640-1660 ℃; the calcination time is preferably 1-2 h, and more preferably 1.5 h; the calcination is preferably carried out under exclusion of air; air is excluded to provide an oxygen-insulating condition.
After the calcination treatment, the product is preferably cooled, crushed and screened to obtain boron carbide; the particle size of the boron carbide is preferably 50-150 μm, more preferably 75-125 μm, and even more preferably 90-100 μm.
The mass ratio of the carbon black to the boric acid is preferably 50-60: 40-50, more preferably 52-58: 42-48, and even more preferably 54-56: 44-46; the particle size of the carbon black is preferably 50 to 150 μm, more preferably 75 to 125 μm, and even more preferably 90 to 100 μm.
The independent particle sizes of the coal powder, the iron powder and the copper oxide powder are preferably 50-150 microns, more preferably 75-125 microns, and even more preferably 90-100 microns.
The pore-forming agent of the present invention preferably comprises oxalic acid and/or tartaric acid; when the pore-forming agent contains both oxalic acid and tartaric acid, the oxalic acid and tartaric acid are preferably mixed in an equal mass ratio.
The invention also provides a preparation method of the iron-carbon-copper alloy micro-electrolysis composite material, which comprises the following steps:
1) mixing boron carbide, coal powder, iron powder, copper oxide powder, a pore-forming agent and water, and then pressing and forming to obtain a formed product;
2) and calcining and quenching the formed product in sequence to obtain the iron-carbon-copper alloy micro-electrolysis composite material.
The mixing time in the step 1) of the invention is preferably 0.5-2 h, and more preferably 1-1.5 h; the pressure for the press molding is preferably 4 to 10MPa, more preferably 6 to 9MPa, and even more preferably 7 to 8 MPa.
The calcination temperature in the step 2) of the invention is preferably 1700-1900 ℃, more preferably 1750-1850 ℃, and more preferably 1800 ℃; the calcination time is preferably 1-2 h, and more preferably 1.5 h; the calcination is preferably carried out under the condition of air isolation, and in the calcination process, the negative pressure in a hearth is preferably 0.1-0.3 MPa, and is further preferably 0.2 MPa; the shaped product is preferably dried before the calcination.
In the calcining process, the copper oxide powder is reduced to generate elemental copper, the elemental copper, iron and carbon are melted to form iron-carbon-copper alloy, and the high-hardness iron-carbon-copper alloy micro-electrolysis composite material is obtained through quenching treatment.
The calcination treatment of the invention leads the interior of the composite material to be in a molten state, and the composite material is condensed and formed again after being cooled, thus the structure of the composite material is compact.
The quenching time in the step 2) is preferably 20-50 s, and more preferably 30-40 s; the medium for quenching treatment is preferably water or sodium chloride solution; the mass concentration of the sodium chloride solution is preferably 0.8-1.2%, and more preferably 1%.
The invention adopts quenching treatment to cool the calcined product; the quenching and cooling can improve the toughness and the strength of the composite material.
The invention also provides application of the iron-carbon-copper alloy micro-electrolysis composite material in wastewater treatment.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1kg of carbon black (with the particle size of 75 microns) and 0.8kg of boric acid are uniformly mixed, then the mixture is calcined under the condition of air isolation, the calcining temperature is 1600 ℃, the calcining time is 1 hour, and the calcined product is cooled, crushed and screened to obtain boron carbide with the particle size of 75 microns.
0.2kg of boron carbide, 1.2kg of iron powder (particle size of 150 μm), 0.37kg of coal powder (particle size of 75 μm), 0.2kg of copper oxide powder (particle size of 125 μm), 0.03kg of tartaric acid and 240mL of water were mixed with stirring for 0.5 hour, and then compression-molded at 6MPa with a tablet press. And (3) drying the formed product, calcining for 1h at 1700 ℃ under the condition of air isolation, wherein the negative pressure in a hearth is 0.3MPa in the calcining process, taking out the calcined product, and quenching and cooling for 30s in water to obtain the iron-carbon-copper alloy micro-electrolysis composite material.
The mass of the iron-carbon-copper alloy micro-electrolysis composite material obtained in the example 1 is 2.1kg, and the crushing strength of the iron-carbon-copper alloy micro-electrolysis composite material is 1300MPa through detection.
1kg of iron-carbon-copper alloy micro-electrolysis composite material is applied to a micro-electrolysis pilot plant as a strengthening pretreatment material of pharmaceutical wastewater, the treatment capacity of the pilot plant is 22L/d, the COD (chemical oxygen demand) of the pharmaceutical wastewater is 7500mg/L, the effluent is reduced to 3000mg/L, the BOD/COD (BOD/COD is the ratio of biological oxygen consumption and chemical oxygen consumption) is increased to 0.35 from 0.06, the biochemical property is obviously improved, and the COD can be fully degraded by microorganisms at the later stage, thereby showing that the original battery effect of the iron-carbon-copper alloy micro-electrolysis composite material is better.
The crushing strength of the iron-carbon-copper alloy micro-electrolysis composite material is still stable to be more than 900MPa after the iron-carbon-copper alloy micro-electrolysis composite material is used for two weeks under the acidic condition that the pH value is 2, the chemical stability is good, and no obvious oxidation hardening exists on the surface.
As shown in fig. 1, an SEM (FEI-Quanta 200 scanning electron microscope) image of the iron-carbon-copper alloy microelectrolytic composite material of example 1 shows, and it can be seen from fig. 1 that the composite material of the present invention has a pore structure and good uniformity.
The topography of the iron carbon copper alloy micro-electrolysis composite material of example 1 is shown in figure 2. As can be seen from FIG. 2, the composite material of the present invention is a cylinder (2 cm. times.1.5 cm) having a porous structure.
The energy spectrum of the iron-carbon-copper alloy microelectrolytic composite material in example 1 is shown in fig. 3, and as can be seen from fig. 3, the composite material of the invention contains iron, carbon, copper and boron elements, and the content of the iron element is the highest.
Example 2
1kg of carbon black (with the particle size of 125 mu m) and 1kg of boric acid are uniformly mixed, then the mixture is calcined under the condition of air isolation, the calcining temperature is 1650 ℃, the calcining time is 2 hours, and the calcined product is cooled, crushed and screened to obtain the boron carbide with the particle size of 125 mu m.
0.15kg of boron carbide, 1.4kg of iron powder (particle size of 75 μm), 0.29kg of coal powder (particle size of 75 μm), 0.15kg of copper oxide powder (particle size of 125 μm), 0.01kg of oxalic acid and 300mL of water were stirred and mixed for 1 hour, and then compression-molded at 4MPa with a tablet press. And (3) drying the formed product, calcining for 2h at 1800 ℃ under the condition of air isolation, wherein the negative pressure in a hearth is 0.2MPa in the calcining process, taking out the calcined product, and quenching and cooling for 40s in water to obtain the iron-carbon-copper alloy micro-electrolysis composite material.
The mass of the iron-carbon-copper alloy micro-electrolysis composite material obtained in the example 2 is 2.05kg, and the crushing strength of the iron-carbon-copper alloy micro-electrolysis composite material is 1200MPa through detection.
1kg of iron-carbon-copper alloy micro-electrolysis composite material is applied to a micro-electrolysis small test device to serve as a reinforced pretreatment material of pharmaceutical wastewater, the treatment capacity of the small test device is 22L/d, the COD (chemical oxygen demand) inlet water of the pharmaceutical wastewater is 50000mg/L, the outlet water is reduced to 10000mg/L, the BOD/COD value is increased to 0.15 from 0.06, the chroma is reduced to 200 times from 25000 times, and the biodegradability is obviously improved, so that the application performance of the iron-carbon-copper alloy micro-electrolysis composite material is good.
The crushing strength of the iron-carbon-copper alloy micro-electrolysis composite material is still stabilized to be more than 900MPa after the iron-carbon-copper alloy micro-electrolysis composite material is used for one month under the acidic condition that the pH value is 2. The detection mass loss after drying is less than 5%, the chemical stability is good, and the surface is free from obvious oxidation hardening.
Example 3
1.1kg of carbon black (with the particle size of 90 mu m) and 0.9kg of boric acid are uniformly mixed, then the mixture is calcined under the condition of air isolation, the calcining temperature is 1700 ℃, the calcining time is 1.5h, and the calcined product is cooled, crushed and sieved to obtain the boron carbide with the particle size of 125 mu m.
0.1kg of boron carbide, 1.5kg of iron powder (particle size: 90 μm), 0.28kg of coal powder (particle size: 75 μm), 0.1kg of copper oxide powder (particle size: 125 μm), 0.02kg of oxalic acid and 280mL of water were stirred and mixed for 0.75 hour, and then compression-molded at 10MPa with a tablet machine. And (3) drying the formed product, calcining for 1h at 1900 ℃ under the condition of air isolation, wherein the negative pressure in a hearth is 0.1MPa in the calcining process, taking out the calcined product, and quenching and cooling for 30s in a sodium chloride solution with the mass concentration of 1% to obtain the iron-carbon-copper alloy micro-electrolysis composite material.
The mass of the iron-carbon-copper alloy micro-electrolysis composite material obtained in the example 3 is 2kg, and the crushing strength of the iron-carbon-copper alloy micro-electrolysis composite material is 950MPa through detection.
1kg of iron-carbon-copper alloy micro-electrolysis composite material is applied to a micro-electrolysis small test device to serve as a strengthening pretreatment material of butanol-octanol production wastewater of a chemical plant, the treatment capacity of the small test device is 24L/d, the COD (chemical oxygen demand) inflow of the butanol-octanol production wastewater is 10000mg/L, the effluent is reduced to 3000mg/L, the COD removal rate can reach more than 70%, the value of BOD/COD is promoted, biochemical aerobic sludge is increased quickly, and then the COD is reduced to within 200mg/L after anaerobic/aerobic treatment, which shows that the application performance of the iron-carbon-copper alloy micro-electrolysis composite material is better.
The crushing strength of the iron-carbon-copper alloy micro-electrolysis composite material is still stable to be more than 1000MPa after the iron-carbon-copper alloy micro-electrolysis composite material is used for three months under the acidic condition that the pH value is 2. The mass loss detected after drying is less than 10%, the iron-carbon-copper alloy micro-electrolysis composite material has good chemical stability during use, no obvious oxidation hardening on the surface, small hardness loss and strong mechanical stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The iron-carbon-copper alloy micro-electrolysis composite material is characterized in that the preparation raw materials of the composite material comprise boron carbide, coal powder, iron powder, copper oxide powder, a pore-forming agent and water;
the mass ratio of the boron carbide, the coal powder, the iron powder, the copper oxide powder and the pore-forming agent is 5-10: 10-20: 60-80: 5-10: 0.5-1.5;
the mass volume ratio of the iron powder to the water is 0.6-0.8 kg: 100-150 mL.
2. The iron-carbon-copper alloy microelectrolytic composite material according to claim 1, wherein the preparation method of the boron carbide comprises the following steps: mixing carbon black and boric acid, and calcining to obtain boron carbide;
the calcining temperature is 1600-1700 ℃, and the time is 1-2 h; the calcination is carried out under the condition of isolating air;
the mass ratio of the carbon black to the boric acid is 50-60: 40-50; the particle size of the carbon black is 50-150 mu m.
3. The iron-carbon-copper alloy microelectrolysis composite material according to claim 1 or 2, wherein the particle sizes of the pulverized coal, the iron powder and the copper oxide powder are 50-150 μm independently.
4. The iron-carbon-copper alloy microelectrolytic composite material according to claim 3, wherein the pore-forming agent comprises oxalic acid and/or tartaric acid.
5. The method for preparing the iron-carbon-copper alloy micro-electrolysis composite material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) mixing boron carbide, coal powder, iron powder, copper oxide powder, a pore-forming agent and water, and then pressing and forming to obtain a formed product;
2) and calcining and quenching the formed product in sequence to obtain the iron-carbon-copper alloy micro-electrolysis composite material.
6. The preparation method according to claim 5, wherein the mixing time in the step 1) is 0.5-2 h, and the pressure for the compression molding is 4-10 MPa.
7. The preparation method of claim 5 or 6, wherein the calcining in the step 2) is carried out at 1700-1900 ℃ for 1-2 h; the calcination is carried out under exclusion of air.
8. The preparation method according to claim 7, wherein the quenching treatment time in the step 2) is 20 to 50 s; the medium for quenching treatment is water or sodium chloride solution.
9. The method according to claim 8, wherein the sodium chloride solution has a mass concentration of 0.8 to 1.2%.
10. Use of the iron-carbon-copper alloy micro-electrolysis composite material according to any one of claims 1 to 4 in wastewater treatment.
CN202111342187.XA 2021-11-12 2021-11-12 Iron-carbon-copper alloy micro-electrolysis composite material and preparation method and application thereof Pending CN113979516A (en)

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