CN112517009A - Modified porous copper-nickel alloy plate and preparation method and application thereof - Google Patents
Modified porous copper-nickel alloy plate and preparation method and application thereof Download PDFInfo
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- CN112517009A CN112517009A CN202011206809.1A CN202011206809A CN112517009A CN 112517009 A CN112517009 A CN 112517009A CN 202011206809 A CN202011206809 A CN 202011206809A CN 112517009 A CN112517009 A CN 112517009A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 104
- 239000000956 alloy Substances 0.000 title claims abstract description 104
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 81
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 47
- 230000015556 catabolic process Effects 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 42
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 238000000576 coating method Methods 0.000 claims description 4
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- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
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- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
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- 230000000694 effects Effects 0.000 description 7
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- SJIHVGHAFMPBSY-UHFFFAOYSA-N O=[Ni].O=[Cu] Chemical compound O=[Ni].O=[Cu] SJIHVGHAFMPBSY-UHFFFAOYSA-N 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J21/185—Carbon nanotubes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/12—Oxidising
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- B01J37/18—Reducing with gases containing free hydrogen
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- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention discloses a modified porous copper-nickel alloy plate and a preparation method and application thereof. The preparation method of the modified porous copper-nickel alloy plate comprises the following steps: uniformly mixing raw materials comprising a polymer binder, a viscosity regulator, copper powder, nickel powder and an organic solvent, then soaking the mixture coated on a carrier plate into a soaking solution, wherein the soaking solution is water or a mixed solution of water and ethanol, then placing the prepared porous copper-nickel alloy plate precursor in an oxygen or air atmosphere and a hydrogen or carbon monoxide atmosphere in sequence for heating, and finally placing the prepared porous copper-nickel alloy plate in a carbon source gas atmosphere for heating to obtain the porous copper-nickel alloy plate. The novel catalytic material provided by the invention is simple to prepare and low in industrial popularization difficulty, the degradation rate and the degradation efficiency are greatly improved when the catalytic material is used for treating VOCs, an additional energy providing device is not required to be provided when the catalytic material is applied, and in addition, the device matched with the modified porous copper-nickel alloy plate provided by the invention is simple in structure, and the application prospect of a catalytic degradation method is greatly expanded.
Description
Technical Field
The invention relates to the field of materials, in particular to a modified porous copper-nickel alloy plate and a preparation method and application thereof.
Background
VOCs refer to a series of volatile organic compounds, and the discharge amount of VOCs in domestic waste gas and industrial waste gas is higher and higher due to the continuous abundance of human daily life and the continuous development of industrialization. However, VOCs may cause certain damage to the human body, and may cause inflammation and pain in eyes, nose, throat, etc., so that people may feel nausea and dizziness, and may increase cancer risk, especially lung cancer, liver cancer, etc.
In the prior art, VOCs are generally degraded by adopting methods such as an adsorption method, a combustion method, catalytic degradation and the like; wherein the adsorption process generates certain hazardous waste; the combustion method is only suitable for treating high-concentration VOCs, the application range is narrow, and the equipment loss is large; the catalytic degradation method, including the photocatalytic degradation method, does not generate hazardous waste, is suitable for treating high-concentration and low-concentration VOCs, but has the advantages of high cost, low efficiency, requirement of an external energy supply device, complex matching device and difficult industrial popularization; in addition, the catalytic materials in the prior art are basically granules or powder, cannot cope with the condition of large-scale treatment, and cannot be widely applied in industry. These drawbacks greatly limit the development of catalytic degradation processes.
Therefore, it would be very significant to provide a new catalytic material with wide application range, low cost, high efficiency, simple matching device and low industrial popularization difficulty.
Disclosure of Invention
The invention aims to solve at least one of the technical problems, and the specific technical scheme is as follows:
a preparation method of a modified porous copper-nickel alloy plate comprises the following steps:
uniformly mixing raw materials including a polymer binder, a viscosity regulator, copper powder, nickel powder and an organic solvent to obtain a premixed solution, coating the premixed solution on a carrier plate, and then soaking the carrier plate in a soaking solution to obtain a porous copper-nickel alloy plate precursor; the soaking solution is water or a mixed solution of water and ethanol; in the premixed liquid, the mass percent of the polymer binder is 3-6%, the mass percent of the viscosity regulator is 1-2%, the mass percent of the organic solvent is 23-37%, and the total mass percent of the copper powder and the nickel powder is 58-70%;
secondly, placing the porous copper-nickel alloy plate precursor in an oxygen or air atmosphere for heating and oxidizing at the temperature of 500-700 ℃; then placing the mixture in a hydrogen or carbon monoxide atmosphere for reduction sintering for 1-3 h, wherein the reduction sintering temperature is 650-850 ℃; preparing a porous copper-nickel alloy plate;
thirdly, heating the porous copper-nickel alloy plate for 40-80 s in a carbon source gas atmosphere to obtain the modified porous copper-nickel alloy plate; the heating temperature is 400-1000 ℃.
The preparation method comprises the steps of mixing a polymer binder, a viscosity regulator and an organic solvent to form a polymer solution, uniformly mixing the polymer solution with copper powder and nickel powder to obtain metal powder slurry with uniformly dispersed copper powder and nickel powder, blade-coating the metal powder slurry on a carrier plate, and then immersing the carrier plate in a soaking solution, wherein the soaking solution can replace the organic solvent, so that the whole system is subjected to phase conversion, the converted material can be cured and molded, and can be directly separated from the carrier plate to form a porous copper-nickel alloy plate precursor; however, the device is not suitable for use in a kitchenThen heating the porous copper-nickel alloy plate precursor in oxygen or air atmosphere, burning off the polymer in the porous copper-nickel alloy plate precursor, oxidizing copper and nickel in the porous copper-nickel alloy plate precursor into copper oxide and nickel oxide, and then heating and reducing the porous copper-nickel alloy plate precursor in hydrogen or carbon monoxide atmosphere; the copper and the nickel are designed to be subjected to the processes of oxidation and reduction together in sequence, so that the metal copper and the metal nickel form intermetallic compounds, and the prepared porous copper-nickel alloy plate has better Cu8Ni3Alloy phase to further improve the VOCs degradation performance (Cu) of the material8Ni3The alloy phase is the key to exerting the degradation performance of the VOCs); and finally, placing the porous copper-nickel alloy plate in a carbon source gas atmosphere to perform in-situ growth of a carbon layer on the surface of the porous copper-nickel alloy plate, so that a carbon material is grown in situ on the surface of the porous copper-nickel alloy plate, and finally preparing the modified porous copper-nickel alloy plate.
In the first step, the pre-mixed liquid is coated on a carrier plate, and then is soaked in the soaking liquid for 6-12 h, which is most suitable; in the second step, the heating and oxidizing time is 2-5 h most preferably.
In the third step, when the heating temperature (namely the in-situ growth temperature of the carbon layer) is 400-600 ℃, amorphous carbon grows in situ on the surface of the porous copper-nickel alloy plate; when the heating temperature (namely the in-situ growth temperature of the carbon layer) is 800-1000 ℃, graphene grows on the surface of the porous copper-nickel alloy plate in situ; and when the heating temperature (namely the in-situ growth temperature of the carbon layer) is other temperature values, the carbon nano tubes are grown on the surface of the porous copper-nickel alloy plate in situ.
The modified porous copper-nickel alloy plate is a brand-new VOCs catalytic degradation material, firstly, the copper-nickel alloy has a catalytic degradation effect on VOCs, but the degradation efficiency is low, and the invention firstly proposes that the prepared porous copper-nickel alloy is used for VOCs catalytic degradation treatment, so that the contact area of VOCs and alloy is increased, and the catalytic degradation effect is improved; on the other hand, the catalytic degradation effect of the porous copper-nickel alloy is greatly improved by growing the carbon material on the surface of the porous copper-nickel alloy in situ (the carbon material has certain adsorption performance and can play a certain role of fixing VOCs), and meanwhile, a certain amount of copper-nickel alloy can be loaded in the carbon layer grown in situ, so that the degradation effect of the catalyst is improved; in addition, in practical application, 5-50V direct current is applied to the modified porous copper-nickel alloy plate, so that the carbon material can generate a temperature of 60-180 ℃, sufficient energy is provided for further improving the degradation treatment effect of VOCs, and additional external energy and a device for providing the external energy in the traditional process are not needed. For convenience of use, in the actual preparation, the porous cupronickel alloy plate in the second step may be placed on a substrate (e.g. a glass plate, etc.) to perform in-situ growth of the carbon material, and in this case, it is ensured that the carbon material is in-situ grown only on the side of the porous cupronickel alloy plate exposed to the carbon source gas.
Preferably, the polymeric binder comprises at least one of polysulfone, polyethersulfone, polyetherimide and polyvinylidene fluoride.
Preferably, the viscosity modifier includes at least one of pyrrolidone, polyvinylpyrrolidone, ethylcellulose and polyethylene glycol. The viscosity regulator is used for regulating the polymer solution to ensure that the copper powder and the nickel powder are uniformly distributed in the metal powder slurry.
Preferably, the organic solvent includes at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
Preferably, the carrier plate comprises one of a glass plate and a ceramic plate.
Preferably, the particle size of the copper powder is 800-1200 μm, and the particle size of the nickel powder is 400-600 nm. The particle sizes of the copper powder and the nickel powder directly influence the aperture, porosity and air permeability of the prepared porous copper-nickel alloy plate.
Preferably, the mass ratio of the copper powder to the nickel powder is 10-20: 1. According to the continuous research of the inventor, the proportion is more favorable for forming a porous structure, and the Cu in the prepared porous copper-nickel alloy plate8Ni3Alloy phase is high, and Cu8Ni3The alloy phase is the key to the degradation treatment of VOCs in the material.
Preferably, the thickness of the premix coated on the carrier plate is 0.2-2 mm.
Preferably, the specific process of step three is as follows: and placing the porous copper-nickel alloy plate in a container, introducing inert gas and hydrogen into the container, heating for 15-25 min at 400-1000 ℃, introducing a carbon source gas, and continuing to heat for 40-80 s. The porous copper-nickel alloy plate is heated in the inert gas and hydrogen atmosphere in advance, so that the influence of the existence of a small amount of metal oxide on the in-situ growth of the carbon material at the later stage can be prevented, and the performance of the prepared modified porous copper-nickel alloy plate is further influenced.
Preferably, in the third step, the total gas flow rate of the hydrogen gas, the inert gas and the carbon source gas is 50 to 300 mL/min. The too high flow velocity can cause the thickness of the carbon material layer on the surface of the porous copper-nickel alloy plate to be too large, and the gas passing efficiency is influenced; too slow a flow rate may result in too small a thickness of the carbon material layer, which may result in incomplete coverage of the surface of the porous cupronickel alloy sheet.
The modified porous copper-nickel alloy plate prepared by the preparation method has a wide application prospect in the field of VOCs degradation.
The invention has the beneficial effects that: the novel catalytic degradation material for VOCs degradation treatment provided by the invention is simple to prepare, low in industrial popularization difficulty, high in degradation rate and degradation efficiency when used for VOCs treatment, and free of an additional heating source and a matched energy supply device when applied.
Drawings
FIG. 1 is an SEM photograph of a cross section of a porous copper-nickel alloy plate precursor at a size of 400 μm;
FIG. 2 is an SEM photograph of the surface of a porous copper-nickel alloy plate precursor at a size of 10 μm;
FIG. 3 is an SEM photograph of the surface of a porous copper oxide-nickel oxide alloy plate at a size of 500 nm;
FIG. 4 is an SEM photograph of a cross section of a porous copper nickel alloy plate at a size of 400 μm;
FIG. 5 is an SEM photograph of the surface of a porous CuNi alloy plate at a size of 10 μm;
FIG. 6 is an SEM photograph of the surface of a modified porous CuNi alloy plate at a size of 1 μm;
FIG. 7 is a schematic view showing the construction of a VOCs degradation treatment apparatus according to example 2;
FIG. 8 is a graph showing the results of degradation rates of formaldehyde gas and ethyl acetate gas when the alloy sheet obtained in comparative example 1 was used as a functional sheet;
FIG. 9 is a graph showing the results of degradation rates of formaldehyde gas and ethyl acetate gas when the alloy sheet obtained in Experimental group 1 was used as a functional sheet;
FIG. 10 is a graph showing the results of degradation rates of formaldehyde gas and ethyl acetate gas when the alloy sheet obtained in example 1 was used as a functional sheet.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described in the following embodiments to fully understand the objects, aspects and effects of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1:
a preparation method of a modified porous copper-nickel alloy plate comprises the following steps:
uniformly mixing polysulfone, pyrrolidone (pvp), copper powder (with the particle size of 1000 microns), nickel powder (with the particle size of 500nm) and N-methylpyrrolidone (NMP) to form metal powder slurry with certain viscosity, wherein in the metal powder slurry, the mass percent of the copper powder is 63%, the mass percent of the nickel powder is 5%, the mass percent of the polysulfone is 5.12%, the mass percent of the viscosity regulator is 1.45%, and the mass percent of the organic solvent is 25.43%; then standing the metal powder slurry in a vacuum drying oven, vacuumizing for 4h for removing bubbles in the metal powder slurry, then scraping and coating the metal powder slurry on a glass flat plate, controlling the thickness to be 0.2-2 mm, then rapidly soaking in water and standing for 8h to prepare a porous copper-nickel alloy plate precursor, wherein electron microscope (SEM) photos are shown in figures 1-2, wherein figure 1 is the SEM photo of the cross section of the porous copper-nickel alloy plate precursor under the size of 400 microns;
FIG. 2 is an SEM photograph of the surface of a porous copper-nickel alloy plate precursor at a size of 10 μm; FIGS. 1-2 can illustrate that the porous copper-nickel alloy plate precursor is well molded, and the copper powder and the nickel powder are uniformly distributed;
placing the porous copper-nickel alloy plate precursor in an atmosphere furnace, introducing oxygen (100mL/min), and heating and oxidizing at 600 ℃ for 3h to obtain a porous copper oxide-nickel oxide alloy plate, wherein FIG. 3 is an SEM (scanning electron microscope) picture of the surface of the porous copper oxide-nickel oxide alloy plate under the size of 500 nm; after the temperature is reduced to room temperature, hydrogen (20mL/min) is introduced, and reduction sintering is carried out for 2h at the temperature of 750 ℃ to prepare a porous copper-nickel alloy plate; the SEM photographs are shown in FIGS. 4-5, wherein FIG. 4 is a SEM photograph of a cross section of the porous CuNi alloy plate at a size of 400 μm; FIG. 5 is an SEM photograph of the surface of a porous CuNi alloy plate at a size of 10 μm; fig. 4 to 5 can show that the prepared porous copper-nickel alloy plate is really porous, and the air permeability of the porous copper-nickel alloy plate is detected to be 6 x 10- 6mol·m-2·s-1·pa-1The aperture is 40 μm, and the porosity is 70%;
and step three, placing the prepared porous copper-nickel alloy plate in an atmosphere furnace, placing the porous copper-nickel alloy plate on a glass substrate, introducing argon (100mL/min) and hydrogen (100mL/min), heating the porous copper-nickel alloy plate at 700 ℃ for 20min, continuously heating the porous copper-nickel alloy plate, and introducing acetylene gas (10mL/min) for 60s to prepare the porous copper-nickel alloy plate with the carbon nano tubes growing on the surface, namely the modified porous copper-nickel alloy plate, wherein FIG. 6 is an SEM photograph of the surface of the modified porous copper-nickel alloy plate under the size of 1 micrometer, and the structure of the carbon nano tubes on the surface of FIG. 6 shows that the prepared porous copper-nickel alloy plate is really modified with the carbon nano tubes on the surface.
Example 2:
changing the heating temperature of the third step in the example 1 to 500 ℃, and preparing a porous copper-nickel alloy plate with amorphous carbon growing in situ on the surface as an experimental group 1 according to the completely same steps and conditions as those in the example 1;
comparative example 1 was set up: a common copper-nickel alloy plate provided with a plurality of through holes is used as a comparative example 1;
the alloy plates prepared in example 1, experimental group 1 and comparative example 1 were used for degradation treatment of VOCs, respectively, and the specific procedures were as follows:
firstly, a VOCs degradation treatment device is designed, the structure of which is shown in FIG. 7, and the VOCs degradation treatment device comprises a reaction chamber 100, wherein the reaction chamber 100 is in a cuboid shape, the length, the width and the height of the reaction chamber 100 are (1-2 m) × (0.8-1.5 m), the reaction chamber 100 is made of stainless steel, a plurality of function boards 500 are arranged inside the reaction chamber 100, the function boards 500 divide the inside of the reaction chamber 100 into at least two sub-chambers 400 which are not communicated with each other, the reaction chamber 100 is provided with an air inlet 200 and an air outlet 300, the function boards 500 are positioned between the air inlet 200 and the air outlet 300, and the air inlet 200 and the air outlet 300 are respectively communicated with; a flow blocking plate 600 is provided between the adjacent function plates 500 so that a shuttle channel is formed in the sub-chamber 400 between the adjacent function plates 500.
The functional plate 500 was subjected to the VOCs degradation treatment experiment using the alloy plates prepared in example 1, experimental group 1, and comparative example 1, respectively, and the steps were as follows:
the formaldehyde gas/ethyl acetate gas is input through the gas inlet 200, after passing through the functional plate 500, due to the existence of the flow blocking plate 600, the advancing route of the formaldehyde gas/ethyl acetate gas in the sub-cavity 400 is back and forth, the advancing route of the formaldehyde gas/ethyl acetate gas is increased, then due to the multi-layer degradation treatment of the functional plate 500, the treated gas is discharged from the gas outlet 300, the treated gas is detected, and the degradation rate of the formaldehyde gas/ethyl acetate gas is calculated.
When the functional board 500 is an alloy board manufactured in the embodiment 1 and the experimental group 1, a direct current voltage is applied to the copper-nickel alloy board layer and the carbon nanotube layer/amorphous carbon layer at normal pressure, wherein the direct current voltage is 5-50V, the positive electrode is connected with the porous copper-nickel alloy layer, the negative electrode is connected with the carbon nanotube layer/amorphous carbon layer, and at this time, due to the application of the current, the carbon nanotube layer/amorphous carbon layer generates a temperature of 60-180 ℃, and energy is provided so that formaldehyde gas/ethyl acetate gas can be catalytically degraded into carbon dioxide and water under the combined action when passing through the porous copper-nickel alloy layer and the carbon nanotube layer/amorphous carbon layer in sequence.
When the functional plate 500 is the alloy plate prepared in the comparative example 1, a direct current voltage of 4-10V is applied to the alloy plate under normal pressure, and the anode and the cathode are both connected to the alloy plate. Because pure copper-nickel alloy has no carbon and low resistance, very high current and short circuit of an instrument can be generated when over-high voltage is applied, and the temperature generated after voltage is applied directly influences the degradation process, only 4-10V is applied when the alloy plate prepared in the comparative example 1 is adopted, and the temperature in the experimental processes of the comparative example 1, the experimental group 1 and the embodiment 1 is kept equivalent.
In addition, in some embodiments, the reaction chamber 100 may be designed to have a cylindrical shape with a length of 1-10 m and a bottom diameter of 0.1-0.25 m, i.e., a tubular shape, and in this case, the degradation process may be performed under a pressurized condition, while in all existing processes, due to the limitations of the catalytic material being in the form of powder/particles and mass processing, a large-sized reaction chamber is generally formed by welding metal parts, and there is no way to ensure the airtightness of the reaction chamber formed by welding, and there is no way to perform the pressurization process; and at this time, the spoiler 600 does not need to be designed to increase the gas traveling path so as to improve the degradation efficiency.
According to the above process, the test results are shown in fig. 8 to 10, in fig. 8, a is a graph showing the result of the degradation rate of formaldehyde gas when the alloy sheet prepared in comparative example 1 is used as the functional sheet 500, and b is a graph showing the result of the degradation rate of ethyl acetate gas when the alloy sheet prepared in comparative example 1 is used as the functional sheet 500; fig. 9 a is a graph showing the results of degradation rate of formaldehyde gas when the alloy sheet manufactured in experimental group 1 was used as the performance sheet 500, and b is a graph showing the results of degradation rate of ethyl acetate gas when the alloy sheet manufactured in experimental group 1 was used as the performance sheet 500; in FIG. 10, a is a graph showing the results of degradation rate of formaldehyde gas when the alloy sheet obtained in example 1 is used as a performance sheet 500, and b is a graph showing the results of degradation rate of ethyl acetate gas when the alloy sheet obtained in example 1 is used as the performance sheet 500.
As can be seen from fig. 8 to 10, the degradation rate of the modified porous copper-nickel alloy plate prepared by the invention for VOCs can reach 98%, which is higher than that of comparative example 1, and meanwhile, the invention firstly proposes that the plate structure is used for degradation treatment of VOCs, compared with the prior art, the industrial popularization difficulty is extremely low, the application range is wider, in addition, in the degradation treatment process, the energy can be provided only by adding 5-50V of direct current voltage, no additional heating source is needed, the cost is greatly saved, the loss of the device is reduced, the matched device provided by the embodiment is also very simple, the production cost is low, and if a reaction chamber with a tubular structure is adopted, degradation treatment of VOCs can be performed under a pressurized condition, and the degradation rate can be greatly increased.
Claims (10)
1. The preparation method of the modified porous copper-nickel alloy plate is characterized by comprising the following steps of:
uniformly mixing raw materials including a polymer binder, a viscosity regulator, copper powder, nickel powder and an organic solvent to obtain a premixed solution, coating the premixed solution on a carrier plate, and then soaking the carrier plate in a soaking solution to obtain a porous copper-nickel alloy plate precursor; the soaking solution is water or a mixed solution of water and ethanol; in the premixed liquid, the mass percent of the polymer binder is 3-6%, the mass percent of the viscosity regulator is 1-2%, the mass percent of the organic solvent is 23-37%, and the total mass percent of the copper powder and the nickel powder is 58-70%;
secondly, placing the porous copper-nickel alloy plate precursor in an oxygen or air atmosphere for heating and oxidizing at the temperature of 500-700 ℃; then placing the mixture in a hydrogen or carbon monoxide atmosphere for reduction sintering for 1-3 h, wherein the reduction sintering temperature is 650-850 ℃; preparing a porous copper-nickel alloy plate;
thirdly, heating the porous copper-nickel alloy plate for 40-80 s in a carbon source gas atmosphere to obtain the modified porous copper-nickel alloy plate; the heating temperature is 400-1000 ℃.
2. The method of claim 1, wherein the polymeric binder comprises at least one of polysulfone, polyethersulfone, polyetherimide, and polyvinylidene fluoride.
3. The method of claim 1, wherein the viscosity modifier comprises at least one of pyrrolidone, polyvinylpyrrolidone, ethylcellulose, and polyethylene glycol.
4. The method according to claim 1, wherein the organic solvent comprises at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
5. The method according to claim 1, wherein the particle size of the copper powder is 800 to 1200 μm, and the particle size of the nickel powder is 400 to 600 nm.
6. The method according to claim 1, wherein the mass ratio of the copper powder to the nickel powder is 10 to 20: 1.
7. The preparation method according to claim 1, wherein the specific process of step three is as follows: and placing the porous copper-nickel alloy plate in a container, introducing inert gas and hydrogen into the container, heating for 15-25 min at 400-1000 ℃, introducing a carbon source gas, and continuing to heat for 40-80 s.
8. The method according to claim 7, wherein the total gas flow rate of the hydrogen gas, the inert gas and the carbon source gas in step three is 50 to 300 mL/min.
9. A modified porous copper-nickel alloy sheet produced by the production method according to any one of claims 1 to 8.
10. Use of a modified porous cupronickel plate according to claim 9 in the field of degradation of VOCs.
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