CN115970670A - Carbon-based supported alumina, preparation method thereof and application thereof in degrading CF (carbon fluoride) 4 In (1) - Google Patents
Carbon-based supported alumina, preparation method thereof and application thereof in degrading CF (carbon fluoride) 4 In (1) Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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Abstract
The invention provides carbon-based alumina, a preparation method thereof and a method for catalytically decomposing CF (carbon fluoride) 4 The application comprises the following steps: s1, mixing a carbon-based material, polyvinylpyrrolidone and an aluminum agent in water to obtain a mixed solution; s2, carrying out hydrothermal treatment on the mixed solution to obtain a heat treatment solution; carrying out solid-liquid separation on the heat treatment liquid to obtain a solid product; drying the solid product to obtain a dried product; and S3, calcining the dried product under the protection of protective atmosphere to obtain the carbon-based loaded alumina. The invention combines the activated carbon and the alumina in a loading mode, so that the catalytic effect of the activated carbon and the alumina is maximized, and the degradation rate of the carbon tetrafluoride is effectively improved. The invention has simple and effective operationRemarkable effect and worth popularizing.
Description
Technical Field
The invention belongs to CF 4 The field of degradation, in particular to carbon-based alumina, a preparation method thereof and CF (carbon fluoride) degradation 4 The use of (1).
Background
CF 4 As a low-carbon halogenated hydrocarbon, the oil-free water-based oil-free water-based oil-based water-based paint has the characteristics of no color, no odor, stable chemical property, oleophobicity and hydrophobicity. Therefore, the composite material is widely applied to the fields of metallurgy, papermaking, packaging, fire extinguishers, pesticides and the like, and the stability of the composite material is derived from the extremely high chemical bond energy of covalent bonds C-F and the high symmetry of the structure of the composite material.
CF as a greenhouse gas 4 The concentration in air is far lower than that of CO 2 But CF 4 The reserve life in the atmosphere is as long as 50000 years, and the Global Warming Potential (GWP) value is CO 2 6500 times of the original product. Thus, a pair of CF is needed 4 The degradation technique of (1).
The low-temperature plasma technology is used as a waste gas treatment technology, and utilizes the effect of a mixture containing high-energy electrons and free radicals generated when gas is broken down by voltage and pollutants in waste gas to decompose pollutant molecules in a very short time so as to achieve the purpose of degrading the pollutants. The low-temperature plasma technology has the advantages of wide application range, large treatment capacity, simple operation and the like.
But the plasma degradation of CF that is currently available 4 The technology of (2) still has the defects of high energy consumption and low degradation efficiency.
Disclosure of Invention
Aims to solve the problem of degrading CF by using a plasma technology in the conventional technology 4 The invention provides a preparation method of carbon-based alumina, which has the technical problems of high energy consumption and low degradation efficiency and comprises the following steps:
s1, mixing a carbon-based material, polyvinylpyrrolidone and an aluminum agent in water to obtain a mixed solution;
the carbon-based material comprises one or more of coal-based activated carbon, conductive carbon black and coconut carbon, and the aluminum agent comprises one or more of aluminum acetate, aluminum nitrate and aluminum chloride;
the mass ratio of the carbon-based material to the aluminum agent is 1: 0.5-2, wherein the mass ratio of the polyvinylpyrrolidone to the aluminum element is 1:0.5 to 2;
s2, carrying out hydrothermal treatment on the mixed solution to obtain a heat treatment solution; carrying out solid-liquid separation on the heat treatment liquid to obtain a solid product; drying the solid product to obtain a dried product;
wherein the temperature of the hydrothermal treatment is 100-240 ℃, and the duration of the hydrothermal treatment is 4-20 h;
and S3, calcining the dried product under the protection of a protective atmosphere to obtain the carbon-based loaded alumina.
Further, the granularity of the carbon-based material is 0.1 mm-10 mm.
Further, the drying process in the step S2 includes the steps of: and (3) alternately cleaning the solid product with water and alcohol for 2-4 times, and then drying to obtain a dry product.
Further, in the step S3, the flow rate of the protective atmosphere is 50 to 500ml/min.
Further, in the step S3, the calcining temperature is 300-800 ℃, the calcining time is 120min, and the calcining temperature rise rate is 5-10 ℃/min
The invention also provides carbon-based aluminum oxide carrier, which is prepared according to the preparation method.
The invention also provides the carbon-based alumina-supported CF for degrading 4 The use of (1).
Further, the carbon-based aluminum oxide is used for degrading CF 4 The application in (1) comprises: carbon-based supported alumina and the CF 4 The flue gas contacts, the low-temperature plasma discharge voltage is set to be 10-70 kv, and the flue gas temperature is 0-300 DEG CLine discharge to the CF 4 Degradation of flue gas, wherein the CF 4 The volume mass ratio of the carbon-based supported alumina to the carbon-based supported alumina is 10-2000 ml:0.1 to 2g.
Further, CF 4 At the CF 4 The volume of the flue gas accounts for 0.01-20%, and the CF 4 The flow rate of the flue gas is 1-200 ml/min.
Further, carbon-based alumina is used for degrading CF 4 The application in (1) further comprises: and carrying out gas washing treatment on the tail gas.
Compared with the prior art, the invention at least comprises the following advantages:
1. the invention refines the raw material proportion, and combines the activated carbon and the alumina in a loading mode by using the technical means of hydrothermal, calcination and the like. Firstly, an aluminum agent is converted into aluminum hydroxide by utilizing a hydrothermal reaction, and the crystalline phase of the aluminum hydroxide is regulated and controlled by changing the temperature and time of the thermal reaction. And then the aluminum hydroxide is partially converted into aluminum oxide through calcination, so that the crystal structure and the grain size of the aluminum are controlled, and the form and the structure of the aluminum oxide are further regulated and controlled. The adsorption effect of the alumina and the activated carbon and the porous structure of the activated carbon are cooperated, so that the alumina and the activated carbon are closely and efficiently combined in a multi-site attachment mode to obtain the carbon-based alumina. The improvement of phase composition and structure strengthens the respective catalytic action of alumina and active carbon, so that the synergistic effect of 1+1 > 2 can be achieved, thereby improving the effect of the carbon-based supported alumina as a catalyst integrally.
2. According to the invention, the carbon-based alumina is combined with the low-temperature plasma technology, on one hand, the low-temperature plasma technology is used for disassembling the C-F bond of carbon tetrafluoride, so that the carbon tetrafluoride is combined with the aluminum atom on the carbon-based alumina to generate AlF, and then the AlF is attached to the surface of the activated carbon (as shown in figure 8), the reaction efficiency is promoted by the phase transformation, and the degradation efficiency is effectively improved. On the other hand, the plasma plays a role of the activated carbon-based alumina-supported catalyst, so that the energy consumption in the plasma degradation process is reduced, the experiment cost and the equipment requirement are reduced, and the feasibility of the scheme is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic diagram of a process for preparing carbon-based alumina according to an embodiment of the present invention.
Fig. 2 is an XRD chart before and after the carbon-based supported alumina prepared in example 1 of the present invention participates in the carbon tetrafluoride degradation reaction.
FIG. 3 is a TEM image of carbon-based alumina prepared in example 1 of the present invention before participating in carbon tetrafluoride degradation reaction.
FIG. 4 is a TEM image of carbon-based alumina prepared in example 1 of the present invention after participating in carbon tetrafluoride degradation reaction.
FIG. 5 is a XPS chart of a carbon-based alumina support prepared in example 1 of the present invention before participating in a carbon tetrafluoride degradation reaction.
FIG. 6 is an XPS chart of carbon-based alumina prepared in example 1 of the present invention after participating in carbon tetrafluoride degradation reaction.
FIG. 7 is a SEM image of a carbon-based alumina support prepared in example 1 of the present invention before participating in a carbon tetrafluoride degradation reaction.
FIG. 8 is an SEM image of carbon-based alumina prepared in example 1 of the present invention after participating in a carbon tetrafluoride degradation reaction.
FIG. 9 is an EDS diagram of a carbon-based alumina support prepared in example 1 of the present invention before participating in a carbon tetrafluoride degradation reaction.
Fig. 10 is an intelligent quantitative result corresponding to an EDS (electronic EDS) chart before the carbon-based alumina-supported catalyst prepared in example 1 of the present invention participates in the carbon tetrafluoride degradation reaction.
FIG. 11 is an EDS diagram of carbon-based alumina prepared in example 1 of the present invention after participating in carbon tetrafluoride degradation reaction.
Fig. 12 is an intelligent quantitative result corresponding to an EDS (electronic EDS) chart of the carbon-based alumina-supported catalyst prepared in example 1 of the present invention after participating in a carbon tetrafluoride degradation reaction.
Fig. 13 is a graph showing the degradation rate with time during the degradation of carbon tetrafluoride according to example 2 of the present invention and comparative examples 1 to 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be based on the realization of the technical solutions by those skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination of the technical solutions should not be considered to exist, and is not within the protection scope claimed by the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
As shown in figure 1, the invention provides a preparation method of carbon-based aluminum oxide, which comprises the following steps:
s1, mixing a carbon-based material, polyvinylpyrrolidone and an aluminum agent in water to obtain a mixed solution.
In some embodiments, the carbon-based material has a major component of activated carbon.
The carbon-based material comprises one or more of coal-based activated carbon, conductive carbon black and coconut carbon, and the aluminum agent comprises one or more of aluminum acetate, aluminum nitrate and aluminum chloride.
Polyvinylpyrrolidone (hereinafter referred to as PVP) is a synthetic water-soluble polymer compound, and has the general properties of a water-soluble polymer compound, such as colloid protection, film-forming property, adhesiveness, hygroscopicity, solubilization or aggregation. Polyvinylpyrrolidone is widely used because it can increase various physicochemical properties of products. In the invention, the polyvinylpyrrolidone has excellent effect, is adsorbed on the surface of the particles to form protection, prevents the particles from coagulating, and forms a structure in the solution to standardize the growth form of the particles.
The particle size of the carbon-based material can be controlled to be 1mm-3mm, and when the particle size of the carbon-based material is controlled to be in this range, the finally prepared carbon-based alumina carrier can be placed in the plasma reactor without causing powder splashing.
Wherein the mass ratio of the carbon-based material to the aluminum agent may be 1: 0.5-2, wherein the mass ratio of the N-vinyl pyrrolidone to the aluminum element can be 1:0.5 to 2. In the mass ratio interval, the aluminum can be dispersed as much as possible, and more active aluminum forms can be obtained.
In some embodiments, the volume of water in the mixed solution may be 80 to 90%.
In other embodiments, the mixed solution can be placed in a magnetic stirring vessel and stirred magnetically for 12 hours, so that the mixed solution is fully stirred.
S2, carrying out hydrothermal treatment on the mixed solution to obtain a heat treatment solution; carrying out solid-liquid separation on the heat treatment liquid to obtain a solid product; and drying the solid product to obtain a dried product.
The heat treatment in step S2 may include the steps of: controlling the mixed solution to perform hydrothermal reaction; pouring the mixed solution into a liner of a pressure relief reaction kettle, and then placing the pressure relief reaction kettle in an oven to heat for 6-8 hours.
Wherein the temperature of the hydrothermal treatment is 100-240 ℃, and the duration of the hydrothermal treatment is 4-20 h.
In other embodiments, the heat treatment solution may be filtered to obtain a solid product, and the obtained solid product is alternately cleaned with pure water and alcohol for 2 to 4 times and then dried in an oven for 10 to 12 hours to obtain a dried product.
And S3, calcining the dried product under the protection of protective atmosphere, and converting the main component of the aluminum agent loaded on the carbon into aluminum oxide to obtain the carbon-based loaded aluminum oxide.
The active carbon and the alumina are combined in a loading mode by means of accurate raw material components and raw material proportion and by means of calcination and the like. The aluminum agent is converted into aluminum hydroxide in the hydrothermal reaction process, the aluminum hydroxide is converted into aluminum oxide in the calcining process, and the phase conversion finally generates the aluminum oxide with good adsorbability and catalytic performance. The porous, adsorptive and catalytic properties of the activated carbon are combined, and finally the loading effect of multi-site efficient close adhesion of the alumina is presented.
In some embodiments, the tube furnace may be evacuated prior to introducing the protective atmosphere to prevent O in the tube furnace 2 Reacts with carbon-based aluminum oxide, and influences the catalytic effect of the oxidant.
In the step S3, the protective atmosphere may be nitrogen, and the flow rate of the protective atmosphere may be 50 to 500ml/min, so that the calcination vessel may be filled with the protective atmosphere in a short time, and oxygen is prevented from being introduced again.
The protective atmosphere can comprise inert gases such as nitrogen, and before the protective atmosphere is introduced, the calcining vessel can be vacuumized, so that the reaction between oxygen in the calcining vessel and the carbon-based aluminum oxide is avoided, and the purity and the catalytic effect of the carbon-based aluminum oxide are ensured.
Illustratively, the calcination vessel may be a tube furnace.
In the step S3, the calcining temperature can be 300-800 ℃, the calcining time can be 120min, and the calcining temperature rise rate is 5-10 ℃/min.
Aluminum hydroxide generated during the hydrothermal reaction is attached to the surface of the porous carbon, and the aluminum hydroxide is partially converted into Al during calcination 2 O 3 . As can be seen from FIG. 7, due to the excellent adsorption property of activated carbon, al generated by hydrothermal reaction and calcination 2 O 3 And Al (OH) 3 Covering the C surface of the porous carbon, and simultaneously, the larger specific surface area of the porous carbon is Al 2 O 3 And Al (OH) 3 Sufficient attachment sites are provided to participate in the catalytic reaction in the subsequent carbon tetrafluoride degradation process, and the catalytic efficiency is effectively improved.
The invention also provides the carbon-based alumina prepared by the preparation method.
The invention refines the raw material proportion, and combines the activated carbon and the alumina in a loading mode by using the technical means of hydrothermal, calcination and the like. Firstly, a hydrothermal reaction is utilized to convert an aluminum agent into aluminum hydroxide, and the crystalline phase of the aluminum hydroxide is regulated and controlled by changing the temperature and time of the hydrothermal reaction. And then, the aluminum hydroxide is partially converted into aluminum oxide by regulating and controlling the calcining temperature, time and atmosphere, so that the crystal structure and the grain size of the aluminum are controlled, the shape and the structure of the aluminum oxide are regulated and controlled, and the aluminum oxide and the activated carbon are closely and efficiently combined in a multi-point attachment mode in cooperation with the adsorption effect of the aluminum oxide and the activated carbon and the porous structure of the activated carbon, so that the carbon-based aluminum oxide is obtained. The improvement of phase composition and structure strengthens the respective catalytic action of alumina and activated carbon, so that the synergistic effect of 1+1 > 2 can be achieved, and the reaction rate is improved.
The invention also provides the carbon-based aluminum oxide carrier for degrading CF 4 The use of (1).
The invention combines the carbon-based aluminum oxide with the low-temperature plasma technology, on one hand, the low-temperature plasma technology disassembles the C-F bond of the carbon tetrafluoride to combine the carbon tetrafluoride with the aluminum atom on the carbon-based aluminum oxide to generate AlF 3 And the solid phase is attached to the surface of the activated carbon (as shown in figure 8), so that the phase transformation promotes the reaction efficiency, and the degradation efficiency is effectively improved. On the other hand, the plasma plays a role of the activated carbon-based alumina-supported catalyst, so that the energy consumption in the plasma degradation process is reduced, the experiment cost and the equipment requirement are reduced, and the feasibility of the scheme is improved.
In some embodiments, the carbon-based alumina supports degradation of CF 4 The application in (1) comprises the following steps:
the carbon-based supported alumina and the CF are reacted 4 The flue gas contacts, the discharge voltage of the low-temperature plasma is set to be 10-70 kv, and the flue gas temperature isDischarging at 0-300 deg.C to obtain CF 4 Degradation of flue gas, wherein the CF 4 The volume mass ratio of the carbon-based supported alumina to the carbon-based supported alumina is 10-2000 ml:0.1 to 2g.
Exemplarily, the carbon-based supported alumina is placed in a plasma reactor, the plasma reactor is opened, and CF is introduced into the plasma reactor 4 Flue gas to obtain degraded CF 4 And (4) the tail gas.
It was previously stated that plasma reactors are one of the important devices in various experimental and application systems. Can be obtained by various modes such as glow discharge under low pressure, radio frequency discharge, microwave discharge, pulse corona discharge under normal pressure, dielectric barrier discharge and the like. Typically, plasma is used in combination with catalysis.
In some embodiments, a dielectric barrier discharge low temperature plasma (hereinafter, referred to as DBD) may be applied, and has become a new technology for waste gas treatment due to the advantages of DBD, such as high efficiency, low energy consumption, wide application range, large treatment capacity, and simple operation. But the plasma degradation CF that is available at present 4 The method still has the technical problems of high temperature, high energy consumption and low degradation efficiency.
Further refined, the low-temperature plasma discharge mode can be annular discharge in dielectric barrier discharge.
Degradation of CF using low temperature plasma 4 In the process, on the one hand, CF 4 Breaking the C-F bond by plasma, wherein F atoms are combined with Al atoms in alumina and aluminum hydroxide loaded on the surface of carbon-based alumina to generate AlF 3 Promote CF 4 Decomposing; on the other hand, the special carbon-based alumina-supported structure after the hydrothermal calcination treatment optimizes the catalytic and adsorptive properties of the alumina and the activated carbon, and the three synergistically generate unexpected improvement effect on the degradation efficiency. The plasma is utilized to activate the catalyst, so that the energy consumption is greatly reduced on the basis of the original plasma catalysis.
Illustratively, the discharge voltage of the plasma reactor is set to 25kv, the discharge mode of the plasma reactor is four-circumference discharge, and the temperature in the plasma reactor is 200-250 ℃.
As yet another example, the CF 4 The volume mass ratio of the carbon-based supported alumina to the carbon-based supported alumina is 10-2000 ml:1 to 2g.
Further, CF 4 At the CF 4 The volume of the flue gas accounts for 0.01-20%, and the CF 4 The flow rate of the flue gas is 1-200 ml/min.
CF can be firstly 4 Mixed in background gas of argon and then introduced into a plasma reactor, thereby ensuring CF 4 CF in flue gas 4 The degradation rate of (c).
In some embodiments, the tail gas may be scrubbed. The tail part of the gas washing bottle mounting sub-plasma reactor filled with pure water is absorbed by residual hydrogen fluoride, and compared with tail gas, the tail gas is directly emptied, so that the scheme is more environment-friendly and has stronger feasibility in tail gas treatment.
To facilitate a further understanding of the invention for those skilled in the art, reference will now be made to the following examples:
some nouns or names in embodiments may be described herein.
Example 1
2g of coconut shell carbon and aluminum acetate, respectively, and 5363 g of PVP (polyvinylpyrrolidone) 0.2645g are weighed, and the coconut shell carbon, the aluminum acetate and the polyvinylpyrrolidone are poured into 100ml of pure water and magnetically stirred for 12 hours to obtain a mixed solution.
Pouring the mixed solution into a reaction kettle, putting the reaction kettle into an oven, and heating at 180 ℃ for 8 hours to carry out hydrothermal treatment to obtain a heat treatment solution. And (4) carrying out suction filtration on the heat treatment liquid to obtain a solid product, washing the solid product with hot water and alcohol alternately for four times, and then drying the washed solid product to obtain a dried product. Pumping the tube furnace to a vacuum state, and introducing N 2 And then the dried product is put into a tubular furnace for heating and calcining to obtain the carbon-based aluminum oxide. Wherein N is 2 The flow rate of the gas introduction is 100ml/min, the calcining temperature is 300 ℃, the heating rate is 5 ℃/min, and the heating time is 120min.
1.5g of the prepared carbon-based alumina is put into a low-temperature plasma reactionIn the reactor, the discharge voltage is adjusted to 25kv, and the flue gas is introduced into the plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then CF is performed in a discharge mode of dielectric barrier discharge 4 Degrading to obtain tail gas after degradation, wherein CF 4 The volume mass ratio of the carbon-based alumina carrier to the carbon-based alumina carrier is 500ml:1g of a catalyst in a reaction vessel 4 The flow rate of the flue gas was 10ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out every five minutes. Measuring CF 4 The highest degradation rate is 64%.
Example 2
2g of coconut shell carbon and 2g of aluminum acetate respectively, 0.2645g of PVP (polyvinylpyrrolidone), and the coconut shell carbon, the aluminum acetate and the N-vinyl pyrrolidone are poured into 100ml of pure water and stirred magnetically for 12 hours to obtain a mixed solution.
Pouring the mixed solution into a reaction kettle, putting the reaction kettle into an oven, and heating for 8 hours at 180 ℃ to carry out hydrothermal treatment to obtain a heat treatment solution. And (4) carrying out suction filtration on the heat treatment liquid to obtain a solid product, washing the solid product with hot water and alcohol alternately for four times, and then drying the washed solid product to obtain a dried product. Pumping the tube furnace to a vacuum state, and introducing N 2 And then the dried product is put into a tubular furnace for heating and calcining to obtain the carbon-based aluminum oxide. Wherein N is 2 The flow rate of the gas introduction is 100ml/min, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, and the heating time is 120min.
1.5g of the prepared carbon-based aluminum oxide is put into a low-temperature plasma reactor, the discharge voltage is adjusted to 25kv, and flue gas is introduced into the plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then CF is performed in a dielectric barrier discharge mode 4 Degrading to obtain tail gas after degradation, wherein CF 4 The volume mass ratio of the carbon-based alumina carrier to the carbon-based alumina carrier is 500ml:1g of a Carbon Fiber (CF) fiber 4 The flow rate of the flue gas was 10ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out every five minutes. Measuring CF 4 The highest degradation rate is 78%.
Example 3
2g of each of coconut charcoal and aluminum acetate, 5363 g of PVP (polyvinylpyrrolidone) 0.2645g, and the coconut charcoal, the aluminum acetate and N-vinylpyrrolidone were poured into 100ml of pure water and magnetically stirred for 12 hours to obtain a mixed solution.
Pouring the mixed solution into a reaction kettle, putting the reaction kettle into an oven, and heating at 180 ℃ for 8 hours to carry out hydrothermal treatment to obtain a heat treatment solution. And (4) carrying out suction filtration on the heat treatment liquid to obtain a solid product, washing the solid product with hot water and alcohol alternately for four times, and then drying the washed solid product to obtain a dried product. Pumping the tube furnace to a vacuum state, and introducing N 2 And then the dried product is put into a tubular furnace for heating and calcining to obtain the carbon-based aluminum oxide. Wherein N is 2 The flow rate of the gas introduction is 100ml/min, the calcining temperature is 800 ℃, the heating rate is 5 ℃/min, and the heating time is 120min.
1.5g of the prepared carbon-based alumina is put into a low-temperature plasma reactor, the discharge voltage is adjusted to 25kv, and flue gas is introduced into the plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then, CF is performed in a discharge mode of dielectric barrier discharge 4 Degrading to obtain tail gas after degradation, wherein CF 4 The volume mass ratio of the carbon-based alumina carrier to the carbon-based alumina carrier is 500ml:1g of a catalyst in a reaction vessel 4 The flow rate of the flue gas was 10ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out every five minutes. Measuring CF 4 The highest degradation rate is 67%.
Example 4
1g of coconut charcoal, 2g of aluminum acetate and 0.529g of PVP (polyvinylpyrrolidone) were weighed, and the coconut charcoal, the aluminum acetate and N-vinylpyrrolidone were poured into 100ml of pure water and magnetically stirred for 12 hours to obtain a mixed solution.
Pouring the mixed solution into a reaction kettle, putting the reaction kettle into an oven, and heating for 6 hours at 200 ℃ to carry out hydrothermal treatment to obtain a heat treatment solution. And (4) carrying out suction filtration on the heat treatment liquid to obtain a solid product, washing the solid product with hot water and alcohol alternately for four times, and then drying the washed solid product to obtain a dried product. Pumping the tube furnace to a vacuum state, and introducing N 2 And then the dried product is put into a tubular furnace for heating and calcining to obtain the carbon-based aluminum oxide. Wherein N is 2 At an inlet flow rate of 150ml/min, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, and the heating time is 120min.
1.5g of the prepared carbon-based alumina is put into a low-temperature plasma reactor, the discharge voltage is adjusted to 25kv, and flue gas is introduced into the plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then, CF is performed in a discharge mode of dielectric barrier discharge 4 Degrading to obtain tail gas after degradation, wherein CF 4 The volume mass ratio of the carbon-based alumina carrier to the carbon-based alumina carrier is 1000ml:1g of a catalyst in a reaction vessel 4 The flow rate of the flue gas was 40ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out every five minutes. Measuring CF 4 The highest degradation rate is 60%.
Referring to comparative examples 1 to 3, the amount or kind of the catalyst in the plasma reactor in example 2 was changed and the remaining steps were not changed as shown in fig. 13.
Comparative example 1
Adjusting the discharge voltage to 25kv, and introducing flue gas into the low-temperature plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then, CF is performed in a manner of dielectric barrier discharge 4 Degrading to obtain tail gas after degradation, wherein CF 4 The flow rate of the flue gas was 10ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out every five minutes. Measuring CF 4 The highest degradation rate is 47%.
Comparative example 2
1.5g of alumina is put into a low-temperature plasma reactor, the discharge voltage is adjusted to 25kv, and flue gas is introduced into the low-temperature plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then, CF is performed in a manner of dielectric barrier discharge 4 Degrading to obtain tail gas after degradation, wherein CF 4 The volume mass ratio of the alumina to the alumina is 500ml:1g of a Carbon Fiber (CF) fiber 4 The flow rate of the flue gas was 10ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out every five minutes. Measuring CF 4 Maximum dropThe dissolution rate was 48%.
Comparative example 3
Placing 1.5g coconut shell carbon into a low-temperature plasma reactor, adjusting the discharge voltage to 25kv, and introducing flue gas into the low-temperature plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then, CF is performed in a discharge mode of dielectric barrier discharge 4 Degrading to obtain tail gas after degradation, wherein CF 4 The volume mass ratio of the coconut shell carbon to the coconut shell carbon is 500ml:1g of a catalyst in a reaction vessel 4 The flow rate of the flue gas was 10ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out once every five minutes. Measuring CF 4 The highest degradation rate is 46%.
Comparative example 4
Putting 0.75g of coconut shell carbon and 0.75g of alumina into a low-temperature plasma reactor, adjusting the discharge voltage to 25kv, and introducing flue gas into the low-temperature plasma reactor, wherein CF 4 At CF 4 The volume of the smoke accounts for 10 percent. Then, CF is performed in a manner of dielectric barrier discharge 4 Degrading to obtain tail gas after degradation, wherein CF 4 The volume mass ratio of the coconut shell carbon to the coconut shell aluminum oxide is 500ml:1g of a catalyst in a reaction vessel 4 The flow rate of the flue gas was 10ml/min.
The tail gas can be detected by a gas chromatograph, and the reading is carried out every five minutes. Measuring CF 4 The highest degradation rate is 60%.
It can be seen from comparative examples 1 to 4 that, when the carbon tetrafluoride is degraded separately or simultaneously by the catalytic and adsorptive actions of alumina and coconut carbon, the effect is inferior to the effect of pure plasma reaction, and the degradation rate of carbon tetrafluoride may be reduced due to the apportionment of energy in the plasma reactor by alumina and coconut carbon; compared with the method, the form and the structure of the aluminum oxide are regulated and controlled by controlling the crystal structure and the grain size of the aluminum through phase transformation and structure change, and the absorption effect of the aluminum oxide and the activated carbon and the porous structure of the activated carbon are cooperated, so that the degradation efficiency of the carbon tetrafluoride is effectively improved, and the degradation energy consumption of the carbon tetrafluoride is reduced.
Analytical example 1
The XRD pattern of the carbon-based alumina-supported material obtained in example 1 is shown in FIG. 2, and it can be seen that the carbon-based alumina-supported material obtained in the present invention has low crystallinity and contains alumina, which proves the synthesis of the carbon-based alumina-supported material in the present invention. Compared with the XRD pattern of carbon-based aluminum oxide carried after carbon tetrafluoride degradation, the crystal C is reduced, and the reaction of C and O is proved to generate CO or CO 2 Overflowing, reacted Al 2 O 3 The crystals produced should be AlF 3 。
As shown in FIGS. 3 to 4, TEM images of the carbon-based supported alumina before and after the reaction were observed, and it was confirmed that the carbon-based supported alumina had a striped lattice, and that alumina crystals were formed, and further, the synthesis of the carbon-based supported alumina material of the present invention was confirmed.
The above-mentioned FIGS. 1 to 3 demonstrate the synthesis of the carbon-based supported alumina of the present invention.
It was determined that the carbon-based supported alumina of example 1 participates in CF 4 XPS Al 2p before and after degradation is shown in FIGS. 5-6, and it can be seen that the carbon-based alumina contains Al 2 O 3 And Al (OH) 3 It was demonstrated that the material produced Al (OH) by hydrothermal reaction 3 . Calcined partial Al (OH) 3 Conversion of Al 2 O 3 ，CF 4 Breaking the C-F bond by plasma, wherein the F atom combines with the Al atom to form AlF 3 Further promote CF 4 And (5) decomposing.
SEM images of the carbon-based supported alumina of example 1 before and after participating in carbon tetrafluoride degradation are shown in FIGS. 7 to 8, from which it can be seen that Al is generated after hydrothermal and calcination 2 O 3 And Al (OH) 3 Covering the surface of porous carbon, and generating new substances on the surface of the carbon-based supported alumina which participates in the degradation reaction of carbon tetrafluoride, namely decomposed C and generated AlF 3 。
As can be seen from figures 9 to 12, by combining the EDS chart before and after the carbon-based alumina in example 1 participates in the carbon tetrafluoride degradation and the corresponding intelligent quantitative result, the content of the C element is increased after the reaction, which proves that CF 4 After decomposition, partial carbon is generated and deposited on the surface of the material, and the O element is reducedLow content of C and O react to produce CO 2 Or CO overflows, and the F element generated on the surface of the material is AlF 3 。
The above-mentioned fig. 5 to 12 can prove the phase change of the surface of the carbon-based supported alumina before and after the reaction, and further prove the propelling effect of the carbon tetrafluoride degradation process by the participation of the carbon-based supported alumina in the carbon tetrafluoride degradation reaction.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.
Claims (10)
1. A preparation method of carbon-based aluminum oxide is characterized by comprising the following steps:
s1, mixing a carbon-based material, polyvinylpyrrolidone and an aluminum agent in water to obtain a mixed solution;
the carbon-based material comprises one or more of coal-based activated carbon, conductive carbon black and coconut carbon, and the aluminum agent comprises one or more of aluminum acetate, aluminum nitrate and aluminum chloride;
the mass ratio of the carbon-based material to the aluminum agent is 1: 0.5-2, wherein the mass ratio of the polyvinylpyrrolidone to the aluminum element is 1:0.5 to 2;
s2, carrying out hydrothermal treatment on the mixed solution to obtain a heat treatment solution; carrying out solid-liquid separation on the heat treatment liquid to obtain a solid product; drying the solid product to obtain a dried product;
wherein the temperature of the hydrothermal treatment is 100-240 ℃, and the duration of the hydrothermal treatment is 4-20 h;
and S3, calcining the dried product under the protection of a protective atmosphere to obtain the carbon-based supported alumina.
2. The method according to claim 1, wherein the particle size of the carbon-based material is 0.1mm to 10mm.
3. The method according to claim 1, wherein the drying process in the step S2 includes the steps of: and (3) alternately cleaning the solid product with water and alcohol for 2-4 times, and then drying to obtain a dry product.
4. The degradation method according to claim 1, wherein in the step S3, the flow rate of the protective atmosphere is 50 to 500ml/min.
5. The degradation method according to claim 1, wherein in the step S3, the calcination temperature is 300-800 ℃, the calcination time is 120min, and the calcination temperature rise rate is 5-10 ℃/min.
6. Carbon-based alumina carrier, characterized by being prepared according to the preparation method of any one of claims 1 to 5.
7. The carbon-based alumina-supported CF as claimed in claim 6 4 The use of (1).
8. The use according to claim 7, comprising: the carbon-based supported alumina and the CF are reacted 4 Contacting with flue gas, discharging the low-temperature plasma under the conditions that the discharge voltage is set to be 10-70 kv and the flue gas temperature is 0-300 ℃, and subjecting the CF to 4 Degradation of flue gas, wherein the CF 4 The volume mass ratio of the carbon-based supported alumina to the carbon-based supported alumina is 10-2000 ml: 0.1-2 g.
9. Use according to claim 8, characterized in that CF 4 At the CF 4 The volume of the flue gas accounts for 0.01-20%, and the CF 4 The flow rate of the flue gas is 1-200 ml/min.
10. The use of claim 8, further comprising: and carrying out gas washing treatment on the tail gas.
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