CN112517009B - 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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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 99
- 239000000956 alloy Substances 0.000 title claims abstract description 99
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 78
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 78
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
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- 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
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
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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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- 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
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B01D—SEPARATION
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- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J37/12—Oxidising
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- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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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- 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, coating the raw materials on a carrier plate, immersing the carrier plate in an immersion liquid, wherein the immersion liquid 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. The novel catalytic material provided by the invention is simple to prepare, low in industrial popularization difficulty, and capable of greatly improving the degradation rate and degradation efficiency when being used for VOCs treatment, and an additional energy supply device is not needed to be provided when the novel catalytic material is applied.
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 are a series of volatile organic compounds, and due to the continuous enrichment of daily life of human beings and continuous development of industrialization, the emission of VOCs in domestic waste gas and industrial waste gas is also higher and higher. VOCs can cause certain injury to human bodies, partial inflammation and pain of eyes, nose, throat and the like are caused by light weight, nausea and dizziness are caused, and cancer risks, especially lung cancer, liver cancer and the like are increased by heavy weight.
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 method can produce certain hazardous waste; the combustion method is only suitable for treating high-concentration VOCs, and has the advantages of narrow application range and large equipment loss; the catalytic degradation method, including the photocatalytic degradation method, is suitable for treating high-concentration and low-concentration VOCs although no hazardous waste is generated, has high cost and low efficiency, needs an external energy supply device, and has complex matched devices and large industrial popularization difficulty; in addition, the catalytic materials in the prior art basically adopt particles 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, the novel catalytic material has the advantages of wide application range, low cost, high efficiency, simple matched device and low industrial popularization difficulty.
Disclosure of Invention
The invention aims to at least solve one of the technical problems, and the specific technical scheme is as follows:
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 to obtain a premix, coating the premix on a carrier plate, and immersing the carrier plate in an immersion liquid to obtain a porous copper-nickel alloy plate precursor; the soaking liquid is water or a mixed solution of water and ethanol; in the premix, the mass percentage of the polymer binder is 3-6%, the mass percentage of the viscosity regulator is 1-2%, the mass percentage of the organic solvent is 23-37%, and the total mass percentage of the copper powder and the nickel powder is 58-70%;
step two, placing the porous copper-nickel alloy plate precursor in an oxygen or air atmosphere for heating and oxidizing, wherein the heating and oxidizing temperature is 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;
step three, placing the porous copper-nickel alloy plate in a carbon source gas atmosphere and heating for 40-80 s to obtain the modified porous copper-nickel alloy plate; the heating temperature is 400-1000 ℃.
According to the invention, a polymer binder, a viscosity regulator and an organic solvent are mixed to form a polymer solution, the polymer solution is uniformly mixed with copper powder and nickel powder to obtain metal powder slurry with uniformly dispersed copper powder and nickel powder, the metal powder slurry is coated on a carrier plate in a scraping way and then immersed in an immersion liquid, the immersion liquid can displace the organic solvent, so that the whole system is subjected to phase conversion, and the converted material is solidified and formed and is directly separated from the carrier plate to form a porous copper-nickel alloy plate precursor; then heating the porous copper-nickel alloy plate precursor in an oxygen or air atmosphere, oxidizing copper and nickel into copper oxide and nickel oxide while burning off polymers in the porous copper-nickel alloy plate precursor, and then heating and reducing the porous copper-nickel alloy plate precursor in a hydrogen or carbon monoxide atmosphere; the design that copper and nickel are sequentially subjected to oxidation and reduction processes together can lead metallic copper and metallic nickel to form intermetallic compounds, so that the prepared porous copper-nickel alloy plate has better Cu 8 Ni 3 Alloy phase, further improving VOCs degradation performance (Cu 8 Ni 3 Alloy phase is the material of choiceKey to degradation performance of VOCs); and finally, placing the porous copper-nickel alloy plate in the atmosphere of carbon source gas to perform in-situ growth of a carbon layer on the surface of the porous copper-nickel alloy plate, so that carbon materials grow on the surface of the porous copper-nickel alloy plate in situ, and finally, the modified porous copper-nickel alloy plate is prepared.
In the first step, the premix solution is coated on a carrier plate, and then immersed in the immersion solution for 6-12 h most suitably; in the second step, the time of heating and oxidizing is most suitable for 2-5 h.
In the third step, amorphous carbon grows on the surface of the porous copper-nickel alloy plate in situ when the heating temperature (namely the carbon layer in-situ growth temperature) is 400-600 ℃; 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 (i.e. the in-situ growth temperature of the carbon layer) is other temperature values, the carbon nano tube grows 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 the VOCs, but the degradation efficiency is lower, and the prepared porous copper-nickel alloy is firstly provided to be used for the catalytic degradation treatment of the VOCs, so that the contact area between the VOCs and the 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 in-situ growth of carbon materials (the carbon materials have certain adsorption performance and can play a role in fixing VOCs) on the surface of the porous copper-nickel alloy, and meanwhile, a certain amount of copper-nickel alloy is loaded in the in-situ grown carbon layer, so that the degradation effect of the catalyst is improved; in addition, in practical application, direct current of 5-50V is added on the modified porous copper-nickel alloy plate, the carbon material can generate temperature of 60-180 ℃, enough energy is provided for further improving the degradation treatment effect of VOCs, and additional external energy and devices for providing external energy in the traditional process are not needed. In order to facilitate the use, in the actual preparation, the porous copper-nickel alloy plate in the second step can be placed on a substrate (such as a glass plate and the like) to perform in-situ growth of the carbon material, and at the moment, the carbon material can be ensured to perform in-situ growth only on the surface of the porous copper-nickel alloy plate exposed to the carbon source gas.
Preferably, the polymer binder includes 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 copper powder and 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 mu m, and the particle size of the nickel powder is 400-600 nm. The particle size of copper powder and nickel powder directly influences the pore diameter, 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 favorable for forming the porous structure, and Cu in the prepared porous copper-nickel alloy plate 8 Ni 3 Alloy phase is relatively high and Cu 8 Ni 3 Alloy phase is the key of degrading VOCs in the material.
Preferably, the thickness of the premix liquid coated on the carrier plate is 0.2-2 mm.
Preferably, the specific process of the third step is as follows: 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 carbon source gas, and continuing heating for 40-80 s. The porous copper-nickel alloy plate is heated in the atmosphere of inert gas and hydrogen in advance, so that the influence of the existence of a small amount of metal oxide on the in-situ growth of a later-stage carbon material can be prevented, and the performance of the prepared modified porous copper-nickel alloy plate is influenced.
Preferably, in the third step, the total gas flow rate of the hydrogen gas, the inert gas and the carbon source gas is 50-300 mL/min. The excessive speed of flow can cause the thickness of the carbon material layer on the surface of the porous copper-nickel alloy plate to be excessive, and the gas passing efficiency is affected; too slow a flow rate may result in too small a layer thickness of the carbon material, possibly resulting in incomplete surface coverage of the porous copper nickel alloy plate.
The modified porous copper-nickel alloy plate prepared by the preparation method has a great application prospect in the field of VOCs degradation.
The beneficial effects of the invention are as follows: 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 being used for VOCs treatment, and free of an additional heating source and a matched energy supply device when being applied.
Drawings
FIG. 1 is a SEM photograph of a porous copper nickel alloy sheet precursor cross section at 400 μm size;
FIG. 2 is an SEM photograph of the surface of a porous copper nickel alloy sheet precursor at a dimension of 10 μm;
FIG. 3 is an SEM photograph of the surface of a porous copper oxide-nickel oxide alloy plate at 500nm size;
FIG. 4 is an SEM photograph of a cross section of a porous copper nickel alloy sheet at 400 μm size;
FIG. 5 is an SEM photograph of the surface of a porous copper nickel alloy sheet at a size of 10 μm;
FIG. 6 is an SEM photograph of the surface of a modified porous copper-nickel alloy sheet at a size of 1 μm;
fig. 7 is a schematic structural diagram of a VOCs degradation treatment apparatus in example 2;
FIG. 8 is a graph showing the degradation rate results of formaldehyde gas and ethyl acetate gas when the alloy sheet produced in comparative example 1 was used as a functional sheet;
FIG. 9 is a graph showing the degradation rate of formaldehyde gas and ethyl acetate gas when the alloy sheet produced in experiment 1 was used as a functional sheet;
FIG. 10 is a graph showing the degradation rate results of formaldehyde gas and ethyl acetate gas when the alloy sheet obtained in example 1 was used as a functional sheet.
Detailed Description
The conception and technical effects of the present invention will be clearly and completely described in conjunction with examples below to fully understand the objects, aspects and effects of the present invention. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
Example 1:
the preparation method of the modified porous copper-nickel alloy plate comprises the following steps:
uniformly mixing polysulfone, pyrrolidone (pvc), copper powder (particle size 1000 mu m), nickel powder (particle size 500 nm) and N-methyl pyrrolidone (NMP) to form metal powder slurry with certain viscosity, wherein in the metal powder slurry, the mass percentage of copper powder is 63%, the mass percentage of nickel powder is 5%, the mass percentage of polysulfone is 5.12%, the mass percentage of viscosity regulator is 1.45%, and the mass percentage of organic solvent is 25.43%; then standing the metal powder slurry in a vacuum drying oven for 4 hours to remove bubbles in the metal powder slurry, then blade-coating the metal powder slurry on a glass flat plate, controlling the thickness to be between 0.2 and 2mm, and then quickly immersing the metal powder slurry in water for standing for 8 hours to obtain a porous copper-nickel alloy plate precursor, wherein an electron microscope (SEM) picture of the porous copper-nickel alloy plate precursor is shown in figures 1-2, and figure 1 is an SEM picture of a cross section of the porous copper-nickel alloy plate precursor at 400 mu m size;
FIG. 2 is an SEM photograph of the surface of a porous copper nickel alloy sheet precursor at a dimension of 10 μm; FIGS. 1-2 can illustrate that the porous copper nickel alloy plate precursor is well formed and the copper powder and the nickel powder are uniformly distributed;
step two, placing a precursor of the porous copper-nickel alloy plate in an atmosphere furnace, introducing oxygen (100 mL/min), heating and oxidizing for 3 hours at 600 ℃ to obtain a porous copper oxide-nickel oxide alloy plate, and taking an SEM (scanning electron microscope) photograph of the surface of the porous copper oxide-nickel oxide alloy plate under the 500nm size as shown in FIG. 3; cooling to room temperature, introducing hydrogen (20 mL/min), and reducing sintering at 750deg.C for 2 hrPreparing a porous copper-nickel alloy plate; the SEM pictures are shown in figures 4-5, wherein figure 4 is an SEM picture of the cross section of the porous copper-nickel alloy plate under the size of 400 mu m; FIG. 5 is an SEM photograph of the surface of a porous copper nickel alloy sheet at a size of 10 μm; FIGS. 4-5 illustrate that indeed porous copper nickel alloy sheets were produced with an air permeability of 6X 10, as measured - 6 mol·m -2 ·s -1 ·pa -1 Pore diameter is 40 μm, and porosity is 70%;
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 (100 mL/min) and hydrogen (100 mL/min), heating at 700 ℃ for 20min, continuously heating and simultaneously introducing acetylene gas (10 mL/min) for 60s to prepare the porous copper-nickel alloy plate with the carbon nano tubes growing on the surface, namely a modified porous copper-nickel alloy plate, wherein FIG. 6 is an SEM (scanning electron microscope) photograph of the surface of the modified porous copper-nickel alloy plate under the size of 1 mu m, and the structure of the carbon nano tubes on the surface of FIG. 6 shows that the prepared porous copper-nickel alloy plate with the carbon nano tubes truly has the surface modified.
Example 2:
the heating temperature of the third step in the example 1 is changed to 500 ℃, and the rest is the same as the step and the condition in the example 1, so that a porous copper-nickel alloy plate with amorphous carbon grown on the surface in situ is prepared as an experimental group 1;
comparative example 1 was set: a general copper-nickel alloy plate provided with a plurality of through holes was used as 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 procedure was as follows:
firstly, designing a VOCs degradation treatment device, the structure of which is shown in figure 7, wherein the VOCs degradation treatment device comprises a reaction chamber 100, the reaction chamber 100 is in a cuboid shape, the length, the width and the height are respectively (1-2 m) (0.8-1.5 m), the reaction chamber 100 is made of stainless steel, a plurality of functional boards 500 are arranged in the reaction chamber 100, the functional boards 500 divide the interior of the reaction chamber 100 into at least two subchambers 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 functional 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 different subchambers 400; the spoilers 600 are provided between the adjacent function boards 500 such that round-trip passages are formed in the subchambers 400 between the adjacent function boards 500.
The function board 500 was subjected to VOCs degradation treatment experiments using the alloy boards prepared in example 1, experimental group 1 and comparative example 1, respectively, as follows:
after formaldehyde gas/ethyl acetate gas is input through the gas inlet 200 and passes through the functional board 500, the traveling path of the formaldehyde gas/ethyl acetate gas in the subchamber 400 is round-trip due to the existence of the flow blocking board 600, the traveling path of the formaldehyde gas/ethyl acetate gas is increased, and then the processed gas is discharged from the gas outlet 300 due to the multi-layer degradation treatment of the functional board 500, so that the degradation rate of the formaldehyde gas/ethyl acetate gas is calculated.
When the functional board 500 is an alloy board prepared in example 1 and experimental group 1, a direct current voltage of 5-50V is needed to be applied to the copper-nickel alloy board layer and the carbon nanotube layer/amorphous carbon layer under normal pressure, wherein the anode is connected with the porous copper-nickel alloy layer, and the cathode is connected with the carbon nanotube layer/amorphous carbon layer, at this time, the carbon nanotube layer/amorphous carbon layer generates a temperature of 60-180 ℃ due to the application of current, and energy is provided to enable formaldehyde gas/ethyl acetate gas to pass through the porous copper-nickel alloy layer and the carbon nanotube layer/amorphous carbon layer in sequence, so that formaldehyde gas/ethyl acetate gas can be catalyzed and degraded into carbon dioxide and water under the combined action.
When the functional plate 500 is the alloy plate produced in comparative example 1, a direct current voltage of 4 to 10V was applied to the alloy plate at the same normal pressure, and both the positive electrode and the negative electrode were connected to the alloy plate. Because pure copper-nickel alloy has no carbon and low resistance, high current can be generated when the alloy is subjected to over-high voltage, and the instrument is short-circuited, and the temperature generated after the voltage is applied in the degradation process is directly influenced, when the alloy plate prepared in comparative example 1 is adopted, only 4-10V is applied, and the temperature in the experimental processes of comparative example 1, experimental group 1 and example 1 is kept to be equivalent.
In addition, in some embodiments, the reaction chamber 100 may be designed in a cylindrical shape, i.e., a tubular shape, having a length of 1-10 m and a bottom diameter of 0.1-0.25 m, and in this case, the degradation treatment process may be performed under a pressurized condition, whereas in all existing processes, due to the limitation of powder/granule form of the catalytic material and mass treatment, it is generally required to weld metal parts to form a large-sized reaction chamber, and the welded reaction chamber has no means to ensure its air tightness and to implement the pressurized treatment; 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 procedure, the results of the test are shown in fig. 8 to 10, in which fig. 8 a is a graph showing 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 degradation rate of ethyl acetate gas when the alloy sheet prepared in comparative example 1 is used as the functional sheet 500; in fig. 9, a is a graph showing the degradation rate of formaldehyde gas when the alloy sheet prepared in experiment set 1 is used as the functional sheet 500, and b is a graph showing the degradation rate of ethyl acetate gas when the alloy sheet prepared in experiment set 1 is used as the functional sheet 500; fig. 10 a is a graph showing the degradation rate of formaldehyde gas when the alloy sheet prepared in example 1 is used as the functional sheet 500, and b is a graph showing the degradation rate of ethyl acetate gas when the alloy sheet prepared in example 1 is used as the functional sheet 500.
As can be seen from FIGS. 8 to 10, the degradation rate of the modified porous copper-nickel alloy plate prepared by the invention to VOCs can reach 98%, which is higher than that of comparative example 1, and meanwhile, the invention provides a plate structure for VOCs degradation treatment for the first time, compared with the prior art, the invention has extremely low industrial popularization difficulty and wider application range, in addition, in the degradation treatment process, the energy can be provided only by adding a direct-current voltage of 5 to 50V, 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 quite simple, the production cost is low, and if the reaction chamber with a tubular structure is adopted, the degradation treatment of the VOCs can be carried out under the pressurized condition, and the degradation rate can be greatly increased.
Claims (6)
1. The preparation method of the modified porous copper-nickel alloy plate is characterized by comprising the following steps of:
uniformly mixing raw materials comprising a polymer binder, a viscosity regulator, copper powder, nickel powder and an organic solvent to obtain a premix, coating the premix on a carrier plate, and immersing the carrier plate in an immersion liquid to obtain a porous copper-nickel alloy plate precursor; the soaking liquid is water or a mixed solution of water and ethanol; in the premix, the mass percentage of the polymer binder is 3-6%, the mass percentage of the viscosity regulator is 1-2%, the mass percentage of the organic solvent is 23-37%, and the total mass percentage of the copper powder and the nickel powder is 58-70%;
step two, placing the porous copper-nickel alloy plate precursor in an oxygen or air atmosphere for heating and oxidizing, wherein the heating and oxidizing temperature is 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;
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 carbon source gas, and continuing heating for 40-80 s;
the grain diameter of the copper powder is 800-1200 mu m, and the grain diameter of the nickel powder is 400-600 nm;
the mass ratio of the copper powder to the nickel powder is 10-20:1;
the total gas flow rate of the hydrogen, the inert gas and the carbon source gas is 50-300 mL/min.
2. The method of preparing according to 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. A modified porous copper-nickel alloy sheet, characterized by being produced by the production method as claimed in any one of claims 1 to 4.
6. The use of a modified porous copper nickel alloy sheet according to claim 5 in the field of degradation of VOCs.
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