Nano-porous blast furnace carbon brick and its preparation method

Abstract

The application discloses a nano-porous blast furnace carbon brick, characterized in that the following raw materials are included: 1-2 parts of graphene alcohol dispersion liquid or aqueous graphene slurry, 55-67 parts of electrically calcined coal aggregate particles, 20-30 parts of graphite crushed aggregate particles, 4-8 parts of silicon powder, 2-5 parts of aluminum oxide powder, and resin; and a preparation method comprises the following steps: S1, preparing the graphene alcohol dispersion liquid or the aqueous graphene slurry, and mixing raw materials to obtain a paste; S2, pressing and curing the paste to obtain a green brick; and S3, loading the green brick into a ring-type calcining furnace for high-temperature calcination, and obtaining the finished nano-porous blast furnace carbon brick after deburring; the graphene is added, and the modified phenolic resin is used in a matched mode, so that the shortcomings that the level of the micro pores in the existing ultra-microporous blast furnace carbon brick is mostly only at the micron level are solved, and the nano-porous blast furnace carbon brick has the characteristics of high micro-pore index, high resistance to molten iron corrosion, high thermal conductivity and high compressive strength.

Description

Technical Field

[0001] This invention belongs to the technical field of refractory material preparation for long-life blast furnace linings, specifically relating to a nanoporous blast furnace carbon brick and its preparation method. Background Technology

[0002] With the rapid modernization and large-scale development of blast furnaces in my country, the production process and physicochemical properties of blast furnace carbon bricks have also developed and improved rapidly. my country's blast furnace carbon bricks have generally reached the world's advanced level. Japan's NDK Corporation has successively developed the BC-10SR, BC-12SR, and BC-15SR series products, with thermal conductivity and other indicators even exceeding 30 W / (m·K). The main methods for improving thermal conductivity are increasing the calcination temperature of the electric calcined coal or the product roasting temperature, as well as adding some graphitic additives. This is reflected in the fluctuation of thermal conductivity with temperature, showing a decreasing trend in the high-temperature range. Domestically produced ultra-microporous carbon bricks also incorporate a certain proportion of graphite to improve their thermal conductivity.

[0003] Currently, the development trend of blast furnace carbon bricks is to maximize thermal conductivity and the proportion of pores smaller than 1 μm. Various additives are often added to the raw materials to improve resistance to molten iron corrosion and microporosity. However, during production, it is crucial to ensure the optimal calcination temperature and time to guarantee the complete conversion of metalloid Si fine powder into SiC and β-phase SiO2, and the complete conversion of Al2O3 and metallic Al into the β-phase, uniformly filling the pores of the carbon brick. Therefore, in addition to improving thermal conductivity and resistance to molten iron corrosion, another important technical indicator for blast furnace carbon bricks is microporosity. Microporosity indicators include permeability, average pore size, and the proportion of pores smaller than 1 μm. The microporosity of refractory materials in the hearth is related to the degree of corrosion, including the penetration of molten iron, chemical corrosion by zinc and alkali metals, and oxidative corrosion by CO2 and water vapor. Improving the microporosity can resist or slow down some corrosion. In addition, improving the microporosity index also helps to improve the mechanical properties of the brick lining, resist the damage caused by molten iron erosion, and reduce the occurrence of "ring cracks" caused by thermal stress.

[0004] The main measures to improve the microporosity of refractory materials are the introduction of elements such as silicon and aluminum, which utilize the whiskers formed during the calcination process to fill the pores. For example, introducing a certain amount of silicon into the raw materials has shown that Si-O-N whiskers are formed during calcination. These whiskers fill the original pore positions, improving the microporosity of the refractory material. However, regardless of the improvement methods, the micropore level mostly remains at the micrometer level, with nanometer-level porosity accounting for a relatively small proportion. Summary of the Invention

[0005] This invention provides a nano-blast furnace carbon brick and its preparation method, which solves the problem that the micropores in existing ultra-microporous blast furnace carbon bricks are mostly limited to the micrometer level.

[0006] The technical solution adopted by this invention to solve its technical problem is: A nanoporous blast furnace carbon brick comprises graphene alcohol dispersion or aqueous graphene slurry, electrically calcined coal aggregate particles, graphite crushed aggregate particles, silicon powder, alumina powder, and resin. The specific raw materials are formulated in the following weight proportions: 1-2 parts of graphene alcohol dispersion or aqueous graphene slurry, 55-67 parts of electrically calcined coal aggregate particles, 20-30 parts of graphite crushed aggregate particles, 4-8 parts of silicon powder, and 2-5 parts of alumina powder.

[0007] Furthermore, the graphene content in the graphene alcohol dispersion or aqueous graphene slurry is 15%-20% by mass; by adding graphene, the graphene is uniformly penetrated into the internal and external structure of the electrically calcined coal aggregate particles and graphite crushed aggregate particles, thereby improving the thermal conductivity and structural strength of the finished bricks.

[0008] Furthermore, the resin is a modified phenolic resin with a viscosity of 25,000-38,000 mPa·s and a curing temperature of 50-180℃. By adding the resin and using it in conjunction with graphene, the graphene can penetrate into the micropores of the electrically calcined coal aggregate particles and the graphite crushed aggregate particles along with the modified phenolic resin, forming a uniform and stable graphene / carbon inclusion.

[0009] Furthermore, it includes the following steps: S1. Raw material mixing: (1) Preparation of graphene alcohol dispersion or aqueous graphene slurry: Prepare graphene alcohol dispersion with a graphene content of 0.15%-0.4% of the total aggregate mass. Disperse 30%-100% of graphene in an alcohol solvent and then uniformly disperse it using an ultrasonic instrument to prepare a graphene alcohol dispersion with a mass fraction of 15%-20%; or use an aqueous graphene slurry with a mass fraction of 15-20%.

[0010] (2) Graphene alcohol dispersion or aqueous graphene slurry, electric calcined coal aggregate particles, graphite crushed aggregate particles, silicon powder and alumina powder are mixed at room temperature according to the proportion to obtain a mixture; by adding silicon powder and alumina powder, Si-O-N whiskers will be formed during the brick firing process. These whiskers fill the original pore positions and improve the microporosity index of the refractory material.

[0011] (3) Add 12.0%-17.0% of resin as a binder to the mixture and knead at room temperature to obtain a paste.

[0012] S2. Making brick blanks: (1) Press the paste into the mold of the vibration molding machine; (2) A vibration molding machine is used to apply pressure and vibration to obtain blast furnace carbon brick blanks; (3) The blast furnace carbon brick blanks are cured at 50-180℃. The curing conditions are: first, raise the temperature to 50℃ and keep it for 2-5 hours, then raise the temperature to 150-180℃ at a rate of 5℃ / hour, and keep it at 150-180℃ for 15-20 hours to obtain the cured carbon brick blanks. S3, Sintering and Shaping: The solidified carbon brick blanks are loaded into a ring furnace for high-temperature roasting, with the highest roasting temperature range being 1350-1420℃. After cooling, roasted carbon brick blanks are obtained, and after deburring, finished nanoporous blast furnace carbon bricks are obtained.

[0013] Furthermore, the graphene alcohol dispersion described in (1) of S1 is prepared from graphene oxide filter cake or graphene powder; the aqueous graphene slurry described in (1) of S1 is prepared from mechanically exfoliated graphene, modified graphene or graphene oxide.

[0014] Furthermore, the graphene particle size D50 in the graphene alcohol dispersion or aqueous graphene slurry described in S1 (1) is controlled within the range of 1-10 μm; by controlling the added graphene particle size, it is possible to make graphene more easily penetrate into the micropores of the electrically calcined coal aggregate particles and the graphite crushed aggregate particles.

[0015] Furthermore, the particle size D50 of graphene in the graphene alcohol dispersion or aqueous graphene slurry described in S1 (1) is controlled within the range of 2-5 μm; the range of 2-5 μm is a more preferred particle size range.

[0016] Furthermore, the alcohol solvent mentioned in (1) of S1 is methanol, ethanol or ethylene glycol.

[0017] Furthermore, in S1(2), the order of adding raw materials is as follows: first, the electric calcined coal aggregate particles and graphite crushed aggregate particles are stirred and mixed to form a mixed aggregate; then, graphene alcohol dispersion or aqueous graphene slurry is sprayed and added while the mixed aggregate is being stirred; then, silicon powder, alumina powder, and resin are added and kneaded to form a paste; adding graphene alcohol dispersion or aqueous graphene slurry by spraying can make graphene uniformly penetrate into the micropores of the aggregate particles.

[0018] Furthermore, the aggregate core is formed by mixing calcined coal aggregate particles with graphite crushed aggregate particles. Graphene alcohol dispersion or aqueous graphene slurry is sprayed onto the outside of the aggregate core. After spraying, mixed powder and resin are used to form the aggregate outer core. The aggregate core and aggregate outer core together form a graphene / carbon inclusion. By controlling the order and method of adding raw materials, a special graphene / carbon inclusion is formed, which significantly reduces the proportion of large pores in the finished brick and improves the finished brick's resistance to molten iron erosion.

[0019] The beneficial effects of this invention are: The nanoporous blast furnace carbon bricks produced by this invention incorporate graphene and are used in conjunction with modified phenolic resin. This allows the graphene to be uniformly infiltrated into the internal and external structures of the electrically calcined coal aggregate particles and graphite crushed aggregate particles, forming a uniform and stable graphene / carbon inclusion. This fully demonstrates the high thermal conductivity and high strength properties of graphene, increasing the compressive strength of the product from 45MPa to 55MPa, the room temperature thermal conductivity from 20Wm / k to 30Wm / k, and the thermal conductivity at 600℃ from 16Wm / k to 25Wm / k, thereby improving the overall performance of the microporous carbon bricks.

[0020] The nanoporous blast furnace carbon bricks produced by this invention, due to the addition of graphene and the use of modified phenolic resin, and by increasing the ceramic phase component and controlling the uniformity of the reaction temperature, allow carbon and silicon to fully react and fill the micropores, resulting in D 50 The 2-5μm sheet-like or wrinkled graphene also penetrates into the micropores along with the modified phenolic resin, greatly reducing the proportion of macropores in the product. The micropore diameter of the product is reduced from 0.1μm to below 0.045μm, the volume ratio of pores smaller than 0.1μm increases from below 30% to over 70%, and the proportion of pores smaller than 1μm reaches over 85%, thereby improving the product's micropore index and enhancing its resistance to molten iron corrosion. The molten iron corrosion resistance index is reduced from about 24% to about 17%.

[0021] Its excellent microporosity, resistance to molten iron corrosion, high thermal conductivity, and high compressive strength make it a suitable replacement for microporous and ultra-microporous carbon bricks in the hearth and taphole. Attached Figure Description

[0022] Figure 1 This is a pore diameter distribution diagram of domestically produced ultra-microporous carbon bricks; Figure 2 This is a diagram showing the pore diameter distribution of the Japanese NDK-8SR carbon brick; Figure 3 This is a pore diameter distribution diagram of the nanoporous blast furnace carbon brick of the present invention. Detailed Implementation

[0023] The technical solution of the present invention will be further described below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0024] A nanoporous blast furnace carbon brick comprises graphene alcohol dispersion or aqueous graphene slurry, electrically calcined coal aggregate particles, graphite crushed aggregate particles, silicon powder, alumina powder, and resin. The specific raw materials are formulated in the following weight proportions: 1-2 parts of graphene alcohol dispersion or aqueous graphene slurry, 55-67 parts of electrically calcined coal aggregate particles, 20-30 parts of graphite crushed aggregate particles, 4-8 parts of silicon powder, and 2-5 parts of alumina powder.

[0025] The graphene content in graphene alcohol dispersions or aqueous graphene slurries is 15%-20% by mass.

[0026] The resin is a modified phenolic resin with a viscosity of 25,000-38,000 mPa·s and a curing temperature of 50-180℃.

[0027] Includes the following steps: S1. Raw material mixing: (1) Preparation of graphene alcohol dispersion or aqueous graphene slurry: Prepare graphene alcohol dispersion with a graphene content of 0.15%-0.4% of the total aggregate mass. Disperse 30%-100% of graphene in an alcohol solvent and then uniformly disperse it using an ultrasonic instrument to prepare a graphene alcohol dispersion with a mass fraction of 15%-20%; or use an aqueous graphene slurry with a mass fraction of 15-20%.

[0028] (2) Graphene alcohol dispersion or aqueous graphene slurry, electric calcined coal aggregate particles, graphite crushed aggregate particles, silicon powder, and alumina powder are mixed at room temperature according to the specified ratio to obtain a mixture; (3) Add 12.0%-17.0% of resin as a binder to the mixture and knead at room temperature to obtain a paste.

[0029] S2. Making brick blanks: (1) Press the paste into the mold of the OTUTA vibration molding machine. The mold specifications are 500*4400mm, 600*4400mm, and 700*3900mm. (2) Use a vibration molding machine to apply pressure and vibration. The parameters of the OTUTA vibration molding machine are set as follows: eccentric angle 85-105°, air bladder pressure 1-3.5MPa, motor speed 1200-1500r / min, vacuum to below 50mbar, apply pressure and vibration for 60-90s to obtain blast furnace carbon brick blanks. (3) The blast furnace carbon brick blanks are cured at 50-180℃. The curing conditions are: first, raise the temperature to 50℃ and keep it for 2-5 hours, then raise the temperature to 150-180℃ at a rate of 5℃ / hour, and keep it at 150-180℃ for 15-20 hours to obtain the cured carbon brick blanks. S3, Sintering and Shaping: The solidified carbon brick blanks are loaded into a ring furnace for high-temperature roasting, and a roasting curve of 320-420 hours is executed. The maximum roasting temperature range is 1350-1420℃. After cooling, the roasted carbon brick blanks are obtained. After deburring, the finished nanoporous blast furnace carbon bricks are obtained.

[0030] Example 1 A nanoporous blast furnace carbon brick, characterized in that it comprises the following raw materials in parts by weight: 1-2 parts of graphene alcohol dispersion or aqueous graphene slurry, 55-67 parts of electrically calcined coal aggregate particles, 20-30 parts of graphite crushed aggregate particles, 4-8 parts of silicon powder, 2-5 parts of alumina powder, and resin.

[0031] Includes the following steps: S1. Raw material mixing: 1) The electric calcined coal aggregate particles and the graphite crushed aggregate particles are stirred and mixed to form a mixed aggregate. Then, graphene alcohol dispersion is sprayed and added while the mixed aggregate is being stirred to obtain a mixture. 2) Add resin to the mixture as a binder, and knead at room temperature to obtain a paste; S2. Making brick blanks: 1) Place the paste into the mold of the OTUTA vibration molding machine for pressing; 2) The parameters of the OTUTA vibration molding machine are set as follows: eccentric angle 95°, air bladder pressure 3MPa, motor speed 1400r / min, vacuuming to below 50mbar, pressure vibration, pre-vibration time 0.5 minutes, and large vibration time 1 minute to obtain blast furnace carbon brick blanks. 3) The blast furnace carbon brick blanks are cured at 80℃. The curing conditions are: first, heat up to 50℃ and hold for 5 hours or 180℃ for 2 hours, then heat up to 180℃ at a rate of 5℃ / hour and hold at 180℃ for 15 hours to obtain the cured carbon brick blanks. S3, Sintering and Shaping: The solidified carbon brick blanks are loaded into a ring furnace for high-temperature roasting, and a roasting curve of 320-420 hours is executed. The maximum roasting temperature is 1420℃. After cooling, the roasted carbon brick blanks are obtained. After deburring, the finished nanoporous blast furnace carbon bricks are obtained.

[0032] Example 2 A nanoporous blast furnace carbon brick and its preparation method, wherein the graphene slurry added to the mixed aggregate in Example 1 has a particle size of 0.15% D. 50The graphene slurry, with a thickness of 5 μm, was prepared by mechanical exfoliation and used with 13% modified phenolic resin with a viscosity of 28000 mPa·s as a binder instead of coal tar pitch binder. The slurry was prepared by vibration molding, low-temperature curing and high-temperature carbonization.

[0033] The prepared nanoporous blast furnace carbon bricks have the following physicochemical properties: Example 3 A nanoporous blast furnace carbon brick and its preparation method, wherein the graphene slurry added to the aggregate in Example 1 has a particle size of 0.4% D. 50 The modified graphene slurry has a thickness of 3.1 μm and is made by using 14% modified phenolic resin with a viscosity of 28000 mPa·s as a binder instead of coal tar pitch binder. It is prepared by vibration molding, low temperature curing and high temperature carbonization process.

[0034] The prepared nanoporous blast furnace carbon bricks have the following physicochemical properties: Example 4 A nanoporous blast furnace carbon brick and its preparation method, wherein the graphene slurry added to the aggregate in Example 1 has a particle size of 0.2% D. 50 It is a 2.3μm graphene oxide slurry, which is used in conjunction with 15% modified phenolic resin with a viscosity of 30000mPa·s as a binder to replace coal tar pitch binder. It is prepared by vibration molding, low temperature curing and high temperature carbonization process.

[0035] The prepared nanoporous blast furnace carbon bricks have the following physicochemical properties: Example 5 A nanoporous blast furnace carbon brick and its preparation method are disclosed. In Example 1, the graphene slurry added to the aggregate has a total content of 0.36% and a particle size D... 50 The modified graphene slurry with a thickness of 5μm and the mechanically exfoliated graphene slurry are used in conjunction with a modified phenolic resin of 15.5% and a viscosity of 30000mPa·s as a binder to replace the coal tar pitch binder. The slurry is prepared by vibration molding, low-temperature curing and high-temperature carbonization process.

[0036] The prepared nanoporous blast furnace carbon bricks have the following physicochemical properties: Example 6 A nanoporous blast furnace carbon brick and its preparation method are disclosed. In step S1 of Example 1, a graphene alcohol dispersion is added to the binder. The graphene alcohol dispersion has a particle size of 0.3% D. 50The 4μm mechanically exfoliated graphene alcohol dispersion is prepared by first dispersing graphene powder in ethylene glycol and then sonicating it to form a graphene alcohol dispersion. The graphene alcohol dispersion is then added to modified phenolic resin in a certain proportion while stirring. After stirring evenly, it is added to a mixture of calcined coal aggregate particles, graphite crushed aggregate particles, silicon powder, and alumina powder. 13.5% of modified phenolic resin with a viscosity of 25000mPa·s is used as a binder to replace coal tar pitch binder. The process is prepared by vibration molding, low-temperature curing, and high-temperature carbonization.

[0037] The prepared nanoporous blast furnace carbon bricks have the following physicochemical properties: Example 7 A nanoporous blast furnace carbon brick and its preparation method are disclosed. In step S1 of Example 1, a graphene alcohol dispersion is added to the binder. The graphene alcohol dispersion has a particle size of 0.36% D. 50 The modified graphene alcohol dispersion with a 2μm diameter is prepared by first dispersing modified graphene powder in ethylene glycol and then sonicating it to form a graphene alcohol dispersion. The graphene alcohol dispersion is then added to modified phenolic resin in a certain proportion while stirring, and stirred evenly. This mixture is then added to a pre-mixed mixture of calcined coal aggregate particles, graphite crushed aggregate particles, silica powder, and alumina powder. 14.5% modified phenolic resin with a viscosity of 28000 mPa·s is used as a binder to replace coal tar pitch binder. The mixture is prepared using vibration molding, low-temperature curing, and high-temperature carbonization processes.

[0038] The prepared nanoporous blast furnace carbon bricks have the following physicochemical properties: Examples 1-5 demonstrate that by adding graphene and using a matching resin, the micropore properties of nanoporous blast furnace carbon bricks are improved, as are their thermal conductivity and resistance to molten iron corrosion and compressive strength. Example 3 added 0.4% modified graphene slurry with a particle size D50 of 3.1 μm, and used 14% modified phenolic resin with a viscosity of 28000 mPa·s. The resulting nanoporous blast furnace carbon bricks exhibited excellent performance in terms of compressive strength, resistance to molten iron corrosion, average pore size, pore volume smaller than 1 μm, and pore volume smaller than 0.1 μm. Examples 6-7, however, did not spray the graphene alcohol dispersion into the mixed aggregate; instead, it was stirred into the modified phenolic resin, which also yielded nanoporous blast furnace carbon bricks with relatively excellent performance. However, compared to Examples 6-7, Examples 1-5 produced nanoporous blast furnace carbon bricks with graphene / carbon inclusions formed by the aggregate core and aggregate outer core, exhibiting superior performance. The nanoporous blast furnace carbon bricks produced by this invention incorporate graphene and are used in conjunction with modified phenolic resin. This allows the graphene to be uniformly infiltrated into the anthracite particles, forming a uniform and stable graphene / carbon inclusion. This fully demonstrates the high thermal conductivity and high strength properties of graphene, increasing the compressive strength of the product from 45MPa to 55MPa, the room temperature thermal conductivity from 20Wm / k to 30Wm / k, and the thermal conductivity at 600℃ from 16Wm / k to 25Wm / k, thus improving the overall performance of the microporous carbon bricks.

[0039] The nanoporous blast furnace carbon bricks produced by this invention, due to the addition of graphene and the use of modified phenolic resin, and by increasing the ceramic phase component and controlling the uniformity of the reaction temperature, allow carbon and silicon to fully react and fill the micropores, resulting in D 50 The 2-5μm sheet-like or wrinkled graphene also penetrates into the micropores along with the modified phenolic resin, greatly reducing the proportion of macropores in the product. The micropore diameter of the product is reduced from 0.1μm to below 0.045μm, the volume ratio of pores smaller than 0.1μm increases from below 30% to over 70%, and the proportion of pores smaller than 1μm reaches over 85%, thereby improving the product's micropore index and enhancing its resistance to molten iron corrosion. The molten iron corrosion resistance index is reduced from about 24% to about 17%.

[0040] Compared with domestically produced ultra-microporous carbon bricks, German SGL-7RND bricks, and Japanese NDK-8SR ultra-microporous carbon bricks, the nanoporous blast furnace carbon bricks exhibit superior or equivalent performance in all aspects. A performance comparison is shown in Table 1. Figure 1-3 ): Table 1. Performance Comparison of Domestic and Foreign Microporous Carbon Bricks Compared with domestically produced microporous carbon bricks, German SGL-7RND bricks, and Japanese NDK-8SR microporous carbon bricks, the nanoporous blast furnace carbon bricks of this invention have certain advantages or are equivalent to foreign products in various performance aspects.

[0041] From the appendix Figure 1-3 It can be seen that, compared with domestically produced ultra-microporous carbon bricks and Japanese NDK-8SR carbon bricks, the blast furnace carbon bricks of the present invention have significantly reduced pores of 100 micrometers to 10 micrometers, greatly increased pores of less than 1 micrometer, with the proportion reaching more than 85%, and the pore volume ratio of less than 0.1μm has increased from less than 30% to more than 70%.

Claims

1. A nanoporous blast furnace carbon brick, characterized in that, The raw materials include the following parts by weight: 1-2 parts of graphene alcohol dispersion or aqueous graphene slurry, 55-67 parts of electro-calcined coal aggregate particles, 20-30 parts of graphite crushed aggregate particles, 4-8 parts of silicon powder, and 2-5 parts of alumina powder; the resin accounts for 12.0%-17.0% of the mass fraction of the mixture of graphene alcohol dispersion or aqueous graphene slurry, electro-calcined coal aggregate particles, graphite crushed aggregate particles, silicon powder, and alumina powder; the mass fraction of graphene in the graphene alcohol dispersion or aqueous graphene slurry is 15%-20%; the resin is a modified phenolic resin with a viscosity of 25000-38000 mPa•s and a curing temperature of 50-180℃. The particle size D50 of graphene in graphene alcohol dispersions or aqueous graphene slurries is controlled within the range of 1-10 μm. The order of adding raw materials is as follows: first, the calcined coal aggregate particles and graphite crushed aggregate particles are stirred and mixed to form a mixed aggregate; then, graphene dispersion or aqueous graphene slurry is sprayed and added while the mixed aggregate is being stirred; and then silicon powder, alumina powder, and resin are added and kneaded to obtain a paste.

2. A method for preparing nanoporous blast furnace carbon bricks according to claim 1, characterized in that, Includes the following steps: S1. Raw material mixing: (1) Preparation of graphene alcohol dispersion or aqueous graphene slurry: Prepare graphene alcohol dispersion with a graphene content of 0.15%-0.4% of the total aggregate mass. Disperse 30%-100% graphene in an alcohol solvent and then uniformly disperse it using an ultrasonic instrument to prepare a graphene alcohol dispersion with a mass fraction of 15%-20%; or use an aqueous graphene slurry with a mass fraction of 15-20%. (2) Graphene alcohol dispersion or aqueous graphene slurry, electrically calcined coal aggregate particles, graphite crushed aggregate particles, silicon powder, and alumina powder are mixed at room temperature according to the specified ratio to obtain a mixture; (3) Add 12.0%-17.0% of resin as a binder to the mixture and knead at room temperature to obtain a paste; The order of adding raw materials is as follows: first, the electric calcined coal aggregate particles and graphite crushed aggregate particles are stirred and mixed to form a mixed aggregate; then, graphene dispersion or aqueous graphene slurry is sprayed and added while the mixed aggregate is being stirred; and then silicon powder, alumina powder, and resin are added and kneaded to obtain a paste. The mixed aggregate formed by the electric calcined coal aggregate particles and the graphite crushed aggregate particles constitutes the aggregate core. Graphene alcohol dispersion or aqueous graphene slurry is sprayed onto the outside of the aggregate core. After spraying, mixed powder and resin are used to form the aggregate outer core. The aggregate core and the aggregate outer core together constitute a graphene / carbon inclusion. S2. Making brick blanks: (1) Press the paste into the mold of the vibration molding machine; (2) A vibration molding machine is used to apply pressure and vibration to obtain blast furnace carbon brick blanks; (3) The blast furnace carbon brick blanks are cured at 50-180℃. The curing conditions are: first, raise the temperature to 50℃ and keep it for 2-5 hours, then raise the temperature to 150-180℃ at a rate of 5℃ / hour, and keep it at 150-180℃ for 15-20 hours to obtain the cured carbon brick blanks. S3, Sintering and Shaping: The solidified carbon brick blanks are loaded into a ring furnace for high-temperature roasting. The maximum temperature range for high-temperature roasting is 1350-1420℃. After cooling, the roasted carbon brick blanks are obtained. After deburring, the finished nanoporous blast furnace carbon bricks are obtained.

3. The method for preparing nanoporous blast furnace carbon bricks according to claim 2, characterized in that, The graphene alcohol dispersion described in (1) of S1 is prepared from graphene oxide filter cake or graphene powder.

4. The method for preparing nanoporous blast furnace carbon bricks according to claim 2, characterized in that, The aqueous graphene slurry described in (1) of S1 is prepared from mechanically exfoliated graphene, modified graphene, or graphene oxide.

5. The method for preparing nanoporous blast furnace carbon bricks according to claim 2, characterized in that, The particle size D50 of graphene in the graphene alcohol dispersion or aqueous graphene slurry described in S1(1) is controlled within the range of 2-5 μm.

6. The method for preparing nanoporous blast furnace carbon bricks according to claim 2, characterized in that, The alcohol solvent mentioned in (1) of S1 is methanol, ethanol or ethylene glycol.

Images