CN114538950A - Porous silicon carbide ceramic skeleton based on biomass powder as carbon source and preparation method thereof - Google Patents
Porous silicon carbide ceramic skeleton based on biomass powder as carbon source and preparation method thereof Download PDFInfo
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000919 ceramic Substances 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 38
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000011148 porous material Substances 0.000 claims abstract description 35
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 58
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- QBKSIHCSDPPLJI-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]tetradecan-1-ol;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCC(CO)N(CCO)CCO QBKSIHCSDPPLJI-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 29
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000005338 heat storage Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
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- 229920002472 Starch Polymers 0.000 description 9
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/573—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
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Abstract
The invention relates to a porous silicon carbide ceramic skeleton based on biomass powder as a carbon source and a preparation method thereof, wherein the porous silicon carbide ceramic skeleton mainly comprises porous silicon carbide ceramic skeletons with different pore forms and arrangement rules, the pore forms mainly comprise layered pores, honeycomb pores, dendritic pores and round pores, the arrangement rules of the pores mainly comprise directional arrangement and random arrangement, the porosity is 50-90%, crystal grains are very compact, the porosity is adjustable, and the porous silicon carbide ceramic skeleton has extremely high heat conductivity coefficient and mechanical strength. The preparation method provided by the invention overcomes the pain point that the high porosity and the compact packing of crystal grains cannot be simultaneously achieved in the traditional silicon carbide framework preparation process, so that the prepared silicon carbide framework is highly ordered, the silicon carbide crystal boundary spacing is extremely small, the heat conductivity coefficient is greatly improved, the process flow is simple, the cost is low, the raw material source is wide, and the preparation method is suitable for large-scale preparation. The porous silicon carbide ceramic framework can be used in the fields of phase change heat storage, building structures, filtering systems and the like.
Description
Technical Field
The invention relates to a porous silicon carbide ceramic skeleton and a preparation method thereof, belonging to the technical field of porous ceramic preparation.
Background
The porous silicon carbide ceramic skeleton is more and more extensive in the field of improving the heat conductivity coefficient of a phase-change material in recent years, but the traditional preparation method is mostly obtained by directly preparing porous biscuit by silicon carbide ceramic powder and a sintering agent and sintering the porous biscuit at high temperature.
The porous silicon carbide ceramic skeleton prepared by directly carbonizing wood, bamboo and the like in the nature as a template and reacting with silicon powder has small gaps among crystal grains and high heat conductivity coefficient and mechanical strength, but the porosity of the porous silicon carbide ceramic skeleton is easily limited by the structure of a biological template, cannot be flexibly adjusted according to application scenes, and is single.
Disclosure of Invention
Aiming at the defects of the prior art and aiming at taking the advantages of the traditional method in porosity adjustment and the advantages of the biological template silicon melting method in grain density into consideration, the invention aims to provide the porous silicon carbide ceramic and the preparation method thereof, wherein the porous silicon carbide ceramic has large adjustability, low cost and high heat conductivity, carbon source powder represented by biomass powder is adopted to prepare a porous blank body by the traditional method and carbonize the porous blank body into the porous carbon blank body so as to reduce the cost problem caused by directly utilizing carbon powder or graphite powder, and then the porous silicon carbide ceramic skeleton is prepared by silicon melting reaction so as to achieve the balance between high heat conductivity and high porosity; it has high heat conductivity, high mechanical strength and flexibly adjustable porosity.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a porous silicon carbide ceramic skeleton based on biomass powder as a carbon source comprises the following steps:
A. adding the raw materials into a solvent, stirring or ball-milling to form slurry; the raw material is a carbon source or a mixture of silicon carbide powder and the carbon source;
B. preparing the slurry into a porous green body by adopting a pore-forming process and carbonizing the porous green body;
C. and carrying out chemical reaction on the carbonized porous blank and silicon powder or silicon dioxide powder to generate the porous silicon carbide ceramic skeleton.
Further, the mass fraction of the added raw materials in the slurry in the step A is 10 wt% to 90 wt%, and particularly preferably 20 wt% to 80 wt%.
Further, the mass ratio of the silicon carbide powder to the carbon source in the mixture of the silicon carbide powder and the carbon source in the step A is 1: 10-10: 1.
Further, the carbon source in the step A mainly comprises plant stem powder, plant fruit powder and resin powder. Such as starch, flour, bamboo powder, wood powder, phenolic resin powder, asphalt powder, the higher the carbon content, the better in principle.
Further, the pore-forming method for preparing the porous blank in the step B comprises a freeze drying technology, a foaming method, a 3D printing method, a pore-forming agent adding method or a polyurethane foam template method. In order to simplify the preparation process and improve the heat conductivity and mechanical properties of the product, freeze drying and foaming methods are particularly preferred.
Further, the solvent of the freeze drying technology comprises water, tert-butyl alcohol, kame and cyclohexane, and the mass percent of the solvent is 10-90 wt%; the solvent of the foaming method is water, the foaming agent comprises yeast, baking soda, lauryl triethanolamine sulfate and detergent, and the content of the foaming agent is 0.01-10 wt%; the solvent of the 3D printing method is photosensitive resin.
And further, the carbonization in the step B is carried out at the temperature of 600-1800 ℃ under the inert atmosphere condition, and the heating rate is 0.1-20 ℃/min.
Furthermore, the feeding mass ratio of the silicon powder or silicon dioxide to the carbonized porous blank in the step C is 1: 1-5: 1, and particularly preferably 3: 1-4: 1.
Further, the method for carrying out chemical reaction with the silicon powder or the silicon dioxide powder in the step C mainly comprises a liquid phase siliconizing method or a gas phase siliconizing method, wherein the temperature range of the reaction of the liquid phase siliconizing method is 1400-2000 ℃, the heating rate is 5-50 ℃/min, the atmosphere environment is vacuum or inert atmosphere, the silicon melting time is 0.5-3 h, the temperature range during silicon removal is 1600-2300 ℃, the heating rate is 5-50 ℃/min, the atmosphere environment is vacuum, and the silicon removal time is 0.5-3 h; the temperature range of the gas phase siliconizing method is 1400-2300 ℃, the temperature rise rate is 1-20 ℃/min, the atmosphere environment is inert atmosphere, and the time is 0.5-10 h.
The porous silicon carbide ceramic skeleton prepared by the method based on the biomass powder as the carbon source comprises lamellar holes, honeycomb holes, dendritic holes and round holes in pore forms; the porosity is 50% -90%.
Compared with the prior art, the invention has the advantages that:
(1) the porous silicon carbide ceramic based on biomass powder as a carbon source and the preparation method thereof overcome the defect that a silicon carbide framework prepared by the traditional process cannot simultaneously have a high porosity and a pain point of tight accumulation of crystal grains, and the prepared silicon carbide framework has high heat conductivity coefficient, small silicon carbide crystal boundary spacing and high mechanical strength, and can effectively improve the performance of the silicon carbide ceramic in the aspect of improving the heat conductivity of a phase-change material.
(2) According to the porous silicon carbide ceramic based on biomass powder as the carbon source and the silicon carbide framework prepared by the preparation method of the porous silicon carbide ceramic, different solvent types and pore-forming methods can be selected according to actual conditions, so that the pore form and the arrangement rule of the porous silicon carbide ceramic are changed, the mass fraction of the carbon source can be flexibly adjusted, the porosity is adjusted, and the requirements of different scenes are met.
(3) The porous silicon carbide ceramic based on biomass powder as the carbon source and the silicon carbide framework prepared by the preparation method of the porous silicon carbide ceramic have the advantages of wide source, large amount, easy obtainment and low cost of the carbon source, and the whole preparation process has low technical threshold, is simple and can be prepared in large scale and in large batch.
Drawings
FIG. 1 is an SEM image of the layered directional pore silicon carbide ceramic skeleton structure prepared in case 1
FIG. 2 is an SEM image of layered oriented pore silicon carbide ceramic skeleton grains prepared in case 1
FIG. 3 is an SEM image of the random pore silicon carbide ceramic skeleton structure prepared in case 3
FIG. 4 is an SEM image of random pore silicon carbide ceramic skeleton grains prepared in example 3
FIG. 5 is an XRD pattern of the porous silicon carbide ceramic frameworks prepared in cases 1 and 3
FIG. 6 shows the rule of variation of thermal conductivity with porosity for porous silicon carbide ceramic frameworks of different porosities prepared in case 1
Detailed Description
Example 1
Weighing a certain mass of the processed cassava starch, adding proper deionized water to form slurry with the mass fraction of 50 wt%, mechanically stirring for half an hour, pouring the slurry into a mold, and drying the slurry in a freeze dryer to form a starch blank with a directional pore structure. And (3) after demoulding the blank, heating to 900 ℃ at the speed of 0.5 ℃/min in a tube furnace in a flowing argon environment, and carbonizing. After carbonization, the carbonized sample is buried in a graphite crucible filled with silicon powder, wherein the mass ratio of silicon to carbon is 3.5: 1. The crucible was then placed in a furnace and allowed to react for 1.5 hours under vacuum at a rate of about 15 c/min to 1600 c to form a silicon carbide and silicon composite. In order to further remove the excessive silicon in the sample, the furnace body is cooled, the temperature of the furnace chamber is raised to 1800 ℃ at the speed of about 15 ℃/min and kept for 1.5h, and the silicon powder is gasified and volatilized in a vacuum environment. It should be noted that, often, such an operation needs more than two times to completely remove the excess silicon, and finally, the silicon powder is completely removed to obtain the silicon carbide ceramic skeleton with the layered oriented pore structure. The directional laminated hole silicon carbide ceramic skeleton with the porosity of 50-90% is obtained by changing the mass fraction of the slurry.
Example 2
Weighing a certain mass of the treated wood powder, adding proper deionized water to form slurry with the mass fraction of 30 wt%, mechanically stirring for half an hour, pouring into a mold, and drying in a freeze dryer to form a starch blank with a directional lamellar pore structure. And (3) after demoulding the blank, heating the blank to 1000 ℃ at the speed of 0.5 ℃/min in a tube furnace in a flowing argon environment, and carbonizing the blank. After carbonization, the carbonized sample is buried in a graphite crucible filled with silicon powder, wherein the mass ratio of silicon to carbon is 4: 1. The crucible was then placed in a furnace and allowed to react for 1.5 hours under vacuum at a rate of about 15 c/min to 1600 c to form a silicon carbide and silicon composite. In order to further remove the excessive silicon in the sample, the furnace body is cooled, the temperature of the furnace chamber is raised to 1800 ℃ at the speed of about 15 ℃/min and kept for 1.5h, and the silicon powder is gasified and volatilized in a vacuum environment. It should be noted that, often, such an operation needs more than two times to completely remove the excess silicon, and finally, the silicon powder is completely removed to obtain the silicon carbide ceramic skeleton with the layered oriented pore structure.
Embodiment 3
5g of dry yeast was dissolved in 115mL of water. After complete dissolution, the mixture was poured into 300 grams of wheat flour, followed by slow kneading by hand for about 15 minutes until a smooth dough was formed, which was then allowed to ferment at 35 ℃ for about 60 minutes to form a random cellular structure. The fermented dough was then placed in a beaker and baked in an oven at 180 ℃ for 40 minutes. And then, sending the dough into an oven at 80 ℃ for drying for 18h, putting the dried bread into a laboratory tubular furnace under the argon gas condition for carbonization after the drying, and heating the blank to 900 ℃ at the speed of 0.5 ℃/min in a flowing argon gas environment in the tubular furnace for carbonization after the blank is demoulded. After carbonization, the carbonized sample is buried in a graphite crucible filled with silicon powder, wherein the mass ratio of silicon to carbon is 3.5: 1. The crucible was then placed in a furnace and allowed to react under vacuum for 1.5 hours at a rate of about 15 c/min to 1600 c to form a silicon carbide and silicon composite. In order to further remove the excess silicon in the sample, the furnace body is cooled, and then the furnace chamber is heated to 1800 ℃ at a speed of about 15 ℃/min and kept for 1.5 hours, and the silicon powder is gasified and volatilized in a vacuum environment. It should be noted that, often, such an operation needs more than two times to completely remove the excess silicon, and finally, the silicon powder is completely removed to obtain the silicon carbide ceramic skeleton with a random pore structure.
Example 4
Weighing a certain mass of the processed cassava starch, adding a proper amount of tert-butyl alcohol to form a slurry with the mass fraction of 20 wt%, mechanically stirring for half an hour, pouring the slurry into a mold, and drying the slurry in a freeze dryer to form a starch blank with an oriented honeycomb-shaped pore structure. And (3) after demoulding the blank, heating to 900 ℃ at the speed of 0.5 ℃/min in a tube furnace in a flowing argon environment, and carbonizing. After carbonization, the carbonized sample is buried in a graphite crucible filled with silicon powder, wherein the mass ratio of silicon to carbon is 3.5: 1. The crucible was then placed in a furnace and allowed to react under vacuum for 1.5 hours at a rate of about 15 c/min to 1600 c to form a silicon carbide and silicon composite. In order to further remove the excess silicon in the sample, the furnace body is cooled, and then the furnace chamber is heated to 1800 ℃ at a speed of about 15 ℃/min and kept for 1.5 hours, and the silicon powder is gasified and volatilized in a vacuum environment. It should be noted that, often, such an operation needs more than two times to completely remove the excess silicon, and finally, the silicon powder is completely removed to obtain the silicon carbide ceramic skeleton with the honeycomb-shaped oriented pore structure.
Example 5
Weighing a certain mass of wood powder, adding proper amount of kame to form slurry with the mass fraction of 40 wt%, mechanically stirring for half an hour, pouring into a mold, and drying in a freeze dryer to form a starch blank with an oriented dendritic pore structure. And (3) after demoulding the blank, heating to 900 ℃ at the speed of 0.5 ℃/min in a tube furnace in a flowing argon environment, and carbonizing. After carbonization, the carbonized sample is buried in a graphite crucible filled with silicon powder, wherein the mass ratio of silicon to carbon is 4: 1. The crucible was then placed in a furnace and allowed to react under vacuum for 1.5 hours at a rate of about 10 c/min to 1600 c to form a silicon carbide and silicon composite. In order to further remove the excess silicon in the sample, the furnace body is cooled, and then the furnace chamber is heated to 1800 ℃ at a speed of about 10 ℃/min and kept for 1.5 hours, and the silicon powder is gasified and volatilized in a vacuum environment. It should be noted that, in many cases, such an operation requires more than two times to completely remove the excess silicon, and finally, the silicon powder is completely removed to obtain the silicon carbide ceramic skeleton with the dendritic oriented pore structure.
Example 6
Weighing a certain mass of wood powder and silicon carbide powder (mass ratio is 1:1), adding proper deionized water to form slurry with the mass fraction of 30 wt%, mechanically stirring for half an hour, pouring into a mold, and drying in a freeze dryer to form a starch blank with a directional lamellar pore structure. And (3) after demoulding the blank, heating to 900 ℃ at the speed of 0.5 ℃/min in a tube furnace in a flowing argon environment, and carbonizing. After carbonization, the carbonized sample is buried in a graphite crucible filled with silicon powder, wherein the mass ratio of silicon to carbon is 4: 1. The crucible was then placed in a furnace and allowed to react under vacuum for 1.5 hours at a rate of about 10 c/min to 1600 c to form a silicon carbide and silicon composite. In order to further remove the excess silicon in the sample, the furnace body is cooled, and then the furnace chamber is heated to 1800 ℃ at a speed of about 10 ℃/min and kept for 1.5 hours, and the silicon powder is gasified and volatilized in a vacuum environment. It should be noted that, in many cases, such an operation requires more than two times to completely remove the excess silicon, and finally, the silicon powder is completely removed to obtain the silicon carbide ceramic skeleton with the dendritic directional laminated pore structure.
Through the implementation example, the porous silicon carbide ceramic skeleton prepared by using starch as a representative carbon source can have a directional lamellar pore, a directional honeycomb pore, a directional kammene pore and a random pore structure according to the change of the type of the solvent and the pore-forming method. No matter what pore form or arrangement structure, the gaps among the crystal grains of the silicon carbide framework are small, the density of the crystal grains is high, the heat conductivity coefficient is high, the porosity is adjustable, the mechanical strength is high, the advantages of the traditional pore forming technology and the silicon melting technology are fully exerted, the preparation method is simple, the cost is low, and the silicon carbide framework can be widely applied to the field of phase change heat storage or other fields.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a porous silicon carbide ceramic skeleton based on biomass powder as a carbon source is characterized by comprising the following steps:
A. adding the raw materials into a solvent, stirring or ball-milling to form slurry; the raw material is a carbon source or a mixture of silicon carbide powder and the carbon source;
B. preparing the slurry into a porous green body by adopting a pore-forming process and carbonizing the porous green body;
C. and carrying out chemical reaction on the carbonized porous blank and silicon powder or silicon dioxide powder to generate the porous silicon carbide ceramic skeleton.
2. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 1, wherein the method comprises the following steps: the mass fraction of the added raw materials in the step A in the slurry is 10-90 wt%.
3. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 1, wherein the method comprises the following steps: and B, in the mixture of the silicon carbide powder and the carbon source in the step A, the mass ratio of the silicon carbide powder to the carbon source is 1: 10-10: 1.
4. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 1, wherein the method comprises the following steps: the carbon source in the step A mainly comprises plant stem powder, plant fruit powder and resin powder.
5. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 1, wherein the method comprises the following steps: and the pore-forming method for preparing the porous blank in the step B comprises a freeze drying technology, a foaming method, a 3D printing method, a pore-forming agent adding method or a polyurethane foam template method.
6. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 5, wherein the method comprises the following steps: the solvent of the freeze drying technology comprises water, tert-butyl alcohol, kame and cyclohexane, and the mass percent of the solvent is 10-90 wt%; the solvent of the foaming method is water, the foaming agent comprises yeast, baking soda, lauryl triethanolamine sulfate and detergent, and the content of the foaming agent is 0.01-10 wt%; the solvent of the 3D printing method is photosensitive resin.
7. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 1, wherein the method comprises the following steps: and B, carbonizing at 600-1800 ℃ under the inert atmosphere condition, wherein the heating rate is 0.1-20 ℃/min.
8. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 1, wherein the method comprises the following steps: and C, the feeding mass ratio of the silicon powder or silicon dioxide to the carbonized porous blank is 1: 1-5: 1.
9. The method for preparing the porous silicon carbide ceramic skeleton based on the biomass powder as the carbon source according to claim 1, wherein the method comprises the following steps: the method for carrying out chemical reaction with the silicon powder or the silicon dioxide powder in the step C mainly comprises a liquid phase siliconizing method or a gas phase siliconizing method, wherein the reaction temperature range of the liquid phase siliconizing method is 1400-2000 ℃, the heating rate is 5-50 ℃/min, the atmosphere environment is vacuum or inert atmosphere, the silicon melting time is 0.5-3 h, the temperature range during silicon removal is 1600-2300 ℃, the heating rate is 5-50 ℃/min, the atmosphere environment is vacuum, and the silicon removal time is 0.5-3 h; the temperature range of the gas phase siliconizing method is 1400-2300 ℃, the temperature rise rate is 1-20 ℃/min, the atmosphere environment is inert atmosphere, and the time is 0.5-10 h.
10. The porous silicon carbide ceramic skeleton prepared by the method according to any one of claims 1 to 9 and based on biomass powder as a carbon source, wherein the porous silicon carbide ceramic skeleton has pore forms including layered pores, honeycomb pores, dendritic pores and round pores; the porosity is 50% -90%.
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