CN111647699A - Carbon block for hearth of blast furnace bottom and manufacturing method thereof - Google Patents
Carbon block for hearth of blast furnace bottom and manufacturing method thereof Download PDFInfo
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- CN111647699A CN111647699A CN202010635166.6A CN202010635166A CN111647699A CN 111647699 A CN111647699 A CN 111647699A CN 202010635166 A CN202010635166 A CN 202010635166A CN 111647699 A CN111647699 A CN 111647699A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B7/00—Blast furnaces
- C21B7/04—Blast furnaces with special refractories
- C21B7/06—Linings for furnaces
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the technical field of refractory materials, in particular to a carbon block for a hearth of a blast furnace bottom and a manufacturing method thereof, which consists of 100 parts of aggregate and 13-20 parts of phenolic resin binder by weight; the aggregate comprises two parts, namely carbonaceous aggregate and non-carbonaceous additive, and the aggregate comprises 68-90 parts of carbonaceous aggregate and 10-32 parts of non-carbonaceous additive in 100 parts of aggregate by weight; wherein the carbonaceous aggregate comprises 70-90% of electrically calcined anthracite and 10-30% of artificial graphite by weight.
Description
Technical Field
The invention relates to the technical field of refractory materials, in particular to a carbon block for a hearth of a blast furnace bottom and a manufacturing method thereof.
Background
The carbon material has low thermal expansion coefficient, high temperature strength, stable volume at high temperature and high resistanceThe material has the characteristics of various medium erosion, excellent heat conducting property and the like, and is widely used as a lining material of high-temperature furnaces such as iron-making blast furnaces, ferroalloy electric furnaces, industrial silicon electric furnaces and the like. The performance of the carbonaceous furnace lining used for the bottom and the hearth of the iron-making blast furnace determines the service life of the first-generation furnace of the blast furnace because the carbonaceous furnace lining is difficult to perform secondary repair under the thermal condition. With the large-scale blast furnace and the progress of smelting technology, the daily output of the blast furnace is greatly improved by intensive smelting measures such as high air temperature, high top pressure, oxygen-enriched air blast, fuel injection and the like. The effective volume of the modern large-scale blast furnace is more than 2000m3The daily molten iron production of unit furnace volume is 2.0-2.5 tons, and the safe, efficient and energy-saving production can be always maintained during the first-generation furnace service period of 15-20 years. Therefore, the performance of the carbon fire-resistant material used as the most critical part of the blast furnace, namely the furnace bottom and the hearth lining, is required to be higher and higher.
Through the analysis of the erosion mechanism of the blast furnace lining brick, the industry consistently believes that the carbon lining has the performances of high volume density, high strength, low porosity and the like of the conventional carbon product, and also has the so-called service performance which is suitable for the special requirements of the iron-making blast furnace, such as excellent alkali erosion resistance, heat conduction performance, oxidation resistance, molten iron erosion resistance, molten iron penetration resistance, thermal shock resistance, slag resistance, a proper micro-pore structure and the like. At present, ultramicropore, high heat conduction and erosion resistance are the development directions of carbon furnace linings.
Generally, a method for producing a carbonaceous refractory material comprises: adding organic binder such as coal pitch and phenolic resin into carbon aggregate such as calcined anthracite, coke, artificial graphite, crystalline flake graphite and soil graphite, kneading, vibration molding (extrusion molding or mould pressing molding), and roasting in coke powder at about 1200 deg.C. If coal tar pitch is used as the binder, the kneading process is carried out at a temperature of 50 to 70 ℃ higher than the softening point of the coal tar pitch.
Researches and experiments show that when the pore diameter of the carbon block is less than 1 mu m, molten iron is difficult to permeate into the carbon block, so that the average pore diameter of the microporous carbon block is less than 1 mu m or even lower. At present, the common microporosity method at home and abroad is to add a proper amount of silicon metal powder into the carbon block ingredients, melt and gasify the silicon at the temperature of more than 1150 ℃, infiltrate, diffuse and redistribute the silicon into cracks and gaps in the carbon block, and react with the carbon to generate beta-SiC. The formed beta-SiC fills cracks and air holes and is deposited on the wall of the air hole, thereby playing the roles of obviously filling the air hole, reducing the aperture of the air hole and reducing the air permeability. On the other hand, the metal silicon powder can modify the binder when the carbon block is roasted, so that the coking value of the binder is improved, and the mechanical property of the carbon block is also improved.
In order to improve the molten iron corrosion resistance of the blast furnace hearth lining material, the aggregate main body of the carbon block mainly adopts electric calcining anthracite with compact structure, and ceramic phase such as alumina, silicon oxide, silicon carbide, silicon nitride, zirconia, magnesia, titanium oxide and the like is added into the ingredients.
Practices prove that the service life of the blast furnace bottom and hearth lining depends on the position of an isothermal line at 1150 ℃, and the adoption of the microporous or ultramicropore carbon block with high heat conductivity can reduce the lining temperature and increase the molten iron viscosity, thereby effectively slowing down the erosion speed of the molten iron on the lining and prolonging the service life of the blast furnace. Generally, the thermal conductivity of carbon blocks is greater than 15W/(m.K), and the carbon does not have the problem of being damaged by thermal stress. In the past, because the heat conductivity coefficient of the common carbon blocks used by the blast furnace is very low and is generally less than 10W/(m.K), ring cracks are easily generated due to the action of thermal stress. The heat conductivity is related to various factors such as the type of raw materials, the compactness of products, the pore structure, the distribution structure of different materials and the like. The heat treatment temperature of the anthracite is increased to ensure that the anthracite is partially graphitized, the reasonable granularity composition and the proper amount of binder are adopted, and the control of the roasting process is an effective way to improve the heat conductivity coefficient of the carbonaceous furnace lining. In addition, the addition of more graphite (artificial graphite or natural graphite) can significantly improve the thermal conductivity of the carbon block, but the addition of flake graphite or artificial graphite can cause the reduction of the strength and other properties of the carbon block. In particular, the artificial graphite belongs to a porous carbon material, and the molten iron corrosion resistance of the artificial graphite is obviously lower than that of the electrocalcined anthracite; in addition, the carbon block added with the crystalline flake graphite is easy to generate delamination cracks in the roasting process, the product percent of pass is influenced, and the product process cost can be improved.
The patent technology of 'a carbon brick for ironmaking blast furnace lining and a preparation method thereof (CN 101514377B)' adopts liquid thermosetting phenolic resin as a binder, and is formed by carrying out normal-temperature mixing and grinding in a mixing and grinding machine, carrying out normal-temperature forming in forming equipment, and then burying carbon in coke powder and roasting. The phenolic resin used as the binder has the advantages that: 1. the method can be used for normal-temperature kneading and normal-temperature molding, and is not like the method that when coal pitch is used as a binder, kneading and molding are carried out at the temperature of 140-170 ℃, temperature control is not strictly needed, the process operation is convenient, and the production cost is saved; 2. the solubility of carbon formed by coking coal pitch to molten iron is high, the solubility of carbon formed by coking phenolic resin to molten iron is low, and the molten iron corrosion performance of the carbon blocks can be improved by using the phenolic resin as a binder; 3. the coke pores formed by coking the coal pitch have more open pores, the pores formed by coking the phenolic resin have more closed pores, and the microporosity rate of the carbon block can be improved by using the phenolic resin as a binder. However, the carbon block using phenolic resin as binder and the patented technology of the preparation process thereof have the following disadvantages: 1. the liquid thermosetting phenolic resin and the aggregate are mixed in a mixing mill, and the mixing effect is poor; 2. the formed carbon block needs to be cured at the temperature of about 120-240 ℃, and cracks are easy to generate in the curing process for the large carbon block; 3. large-size products are difficult to produce by using a patent technology; 4. the carbon formed by coking the phenolic resin has low thermal conductivity coefficient, so the carbon block using the phenolic resin as the binder has low high-temperature strength and poor thermal shock resistance; 5. Only small-sized experimental products can be produced. It is necessary to use a modified phenolic resin.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a carbon block for a hearth of a blast furnace bottom, which can improve the high-temperature strength and the thermal shock resistance of the carbon block and also can improve the heat conduction performance of the carbon block.
The invention also aims to provide a method for manufacturing the carbon block for the hearth of the blast furnace bottom.
The carbon block for the hearth of the blast furnace bottom consists of 100 parts of aggregate and 13-20 parts of phenolic resin binder by weight;
the aggregate comprises two parts, namely carbonaceous aggregate and non-carbonaceous additive, and the aggregate comprises 68-90 parts of carbonaceous aggregate and 10-32 parts of non-carbonaceous additive in 100 parts of aggregate by weight;
wherein the carbonaceous aggregate comprises 70-90% of electrically calcined anthracite and 10-30% of artificial graphite by weight.
The invention relates to a carbon block for a blast furnace bottom hearth, wherein a non-carbonaceous additive comprises one or a mixture of more than two of metal silicon powder and alumina powder (alpha-Al 2O3 micro powder, white corundum powder, brown corundum powder and the like), silicon carbide powder (alpha-SiC or beta-SiC), titanium oxide powder (anatase type or rutile type) and zirconia powder, the metal silicon powder accounts for 30-70% by weight, the mixture of one or more than two of the alumina powder, the silicon carbide powder, the titanium oxide powder and the zirconia powder accounts for 30-70% by weight, the chemical purity of the non-carbonaceous additive is more than 95% by weight, the granularity is 0.045mm (325 meshes) standard sieve for sieving, and the part smaller than 0.045mm (325 meshes) is more than 95% by weight.
The invention relates to a carbon block for a hearth of a blast furnace bottom, which comprises the following components in parts by weight: 8-11% of free phenol, 0.6-0.7% of free aldehyde, 3-6% of water, 77-82% of solid content, 46-50% of carbon residue rate, 8000-10000mPa.s of viscosity (25 ℃), 550-650 of molecular weight; the preparation method of the phenolic resin binder comprises the following steps: weighing the following raw materials in parts by weight: adding 35-40% of pure lignin, 29-32% of phenol, 32.5-30.2% of formaldehyde and 0.5-0.8% of sodium hydroxide into a reaction kettle; opening an emptying valve at the top end of the horizontal condenser, controlling the condensing water pressure of the condenser to be between 0.3MPa and 0.4MPa, and then opening a temperature rising switch to introduce steam into a reaction kettle jacket; stirring and heating up to the initial temperature of not more than 30 ℃, heating up to 80 ℃, strictly controlling the heating speed to be 1 ℃ per 1min, controlling the heating up time to be within 60-70min, heating up to 93-95 ℃, then preserving heat for 90min, cooling to 45 ℃, and discharging to obtain the phenolic resin binder.
The invention relates to a carbon block for a hearth of a blast furnace bottom, which comprises the following components in percentage by weight after electrically calcined anthracite and artificial graphite are mixed: 0-12% of-8 +4, 10-15% of-4 +2, 14-19% of-2 +1, 7-12% of-1 +0.5, 12-17% of-0.5 +15, 8-13% of-0.15 +0.075 and 21-26% of-0.075.
The invention relates to a method for manufacturing carbon blocks for a hearth of a blast furnace bottom, which comprises the following steps:
s1, crushing, grinding and screening the carbon aggregate electrically-forged anthracite and the artificial graphite, and then mixing the materials according to the raw material proportion and the granularity composition requirement, wherein the non-carbon additive is mixed together according to the proportion requirement;
s2, adding the prepared aggregate into a powerful mixing and kneading machine, dry-mixing at a high speed for 1-3 minutes, adding the phenolic resin binder, and wet-mixing for 10-15 minutes, wherein no additional heating is needed to be carried out on the paste in the mixing process, but because the mechanical energy is converted into heat energy in the high-speed mixing process and the chemical reaction is carried out in the mixing process, the temperature of the paste can be raised to 40-60 ℃, and the product quality cannot be influenced;
s3, discharging the mixed paste from the powerful kneader into a disc feeder below the powerful kneader, and uniformly discharging the paste into a forming die below the powerful kneader through the disc feeder;
s4, carrying out compression molding on the paste which is uniformly distributed in the mold on a compression molding machine;
s5, after the molding procedure is finished, drying and curing the molded carbon block product and the tray together;
and S6, machining according to the blast furnace masonry requirements to obtain the ultramicropore carbon brick for the hearth of the blast furnace bottom.
The invention relates to a method for manufacturing a carbon block for a hearth of a blast furnace bottom, which comprises the following steps of S4 molding, forming and vacuumizing a device, wherein the vacuum degree of a vacuum tank is required to be more than-0.09 MPa, and the vacuum degree during working is required to be more than-0.08 MPa: after the material is finished, the die enters a forming station with a paste, a vacuum cover falls down and is pressed tightly, vacuumizing is started, after vacuumizing is carried out for 30-60s, an upper punch of a die press moves downwards to press, pressure maintaining is carried out after the pressure is uniformly increased to a target pressure, the pressure maintaining time is 30-60s, pressure relief is carried out after pressing is finished, vacuum is removed, the upper punch is lifted, the die moves out of the forming station, a demolding station is reached, a carbon block is ejected to a tray, and the forming process is finished.
The invention relates to a method for manufacturing carbon blocks for a hearth of a blast furnace bottom, which comprises the following steps of drying and solidifying in the step S5: after molding, the carbon block which cannot be lifted in strength and the tray enter a drying kiln together, in the drying kiln, at the temperature of 60-80 ℃, phenolic resin in the carbon block gradually undergoes molecular condensation to remove water, and after drying and dehydration for 36-72 hours, although the resin in the carbon block is not completely cured, the carbon block has certain strength and can be lifted out of a hoisting furnace; and hoisting the dried carbon block in the semi-solidified state, and putting the carbon block into a ring type roasting furnace for roasting.
Compared with the prior art, the invention has the beneficial effects that: 1. according to the invention, the pure lignin modified liquid thermosetting phenolic resin is used as the carbon block binder, the pure lignin can be completely combined with the phenolic resin, the performance of the pure lignin is closer to that of coal tar pitch, the high-temperature strength and the thermal shock resistance of the carbon block can be improved, and the heat conductivity of the carbon block can also be improved;
2. according to the invention, the pure lignin modified liquid thermosetting phenolic resin is used as the carbon block binder, and the pure lignin modified phenolic resin can effectively reduce the viscosity of the resin used as the binder, reduce the resin consumption, reduce the production cost and improve the kneading uniformity;
3. the invention uses a pure lignin modified liquid thermosetting phenolic resin as a carbon block binder, most coke air holes generated by coking the binder are closed air holes, the volume of the carbon block holes smaller than 1 mu m can be increased to more than 85%;
4. the invention adopts the processes of normal-temperature kneading and normal-temperature molding, simplifies the process operation process and reduces the production cost;
5. the invention adopts a special high-speed powerful kneader and a matched disc feeder of German Airiser company, so that the kneaded paste is uniform, the molding is facilitated, and the density of the final product and the uniformity of the internal structure are improved;
6. the invention adopts a 4000-year 7000-ton large-tonnage compression molding machine, and can mold large-size carbon block products with the length of 2000-year 4000mm, the width of 400-year 700mm and the height of 400-year 700 mm;
7. the forming machine adopted by the invention is provided with a simulated bidirectional pressing function and a vacuumizing device, so that the density of the formed carbon block product is uniform from top to bottom, and cracks are not generated due to elastic aftereffect;
8. the invention combines the low-temperature semi-curing drying process in the drying kiln with the further slow curing process in the roasting furnace, thereby facilitating the handling of the carbon block green block and avoiding the problem that the large-size products are easy to crack in the curing process when the phenolic resin is used as the binder.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1:
raw materials: the aggregate-phenolic resin composite material comprises 100 parts of aggregate and 13 parts of phenolic resin binder by weight;
the aggregate comprises two parts, namely carbonaceous aggregate and non-carbonaceous additive, and 68 parts of the carbonaceous aggregate and 32 parts of the non-carbonaceous additive are contained in 100 parts of the aggregate by weight;
the carbonaceous aggregate comprises 70% of electrically calcined anthracite and 30% of artificial graphite by weight.
The non-carbonaceous additive comprises 70% of metal silicon powder and one or a mixture of more than two of alumina powder (alpha-Al 2O3 micro powder, white corundum powder, brown corundum powder and the like), silicon carbide powder (alpha-SiC or beta-SiC), titanium oxide powder (anatase type or rutile type) and zirconia powder, wherein the mixture of one or more than two of the alumina powder, the silicon carbide powder, the titanium oxide powder and the zirconia powder accounts for 30% by weight, the chemical purity of the non-carbonaceous additive is more than 95% by weight, the particle size is sieved by a 0.045mm (325 mesh) metric standard sieve, and the part smaller than 0.045mm (325 mesh) is more than 95% by weight.
The phenolic resin binder comprises the following components in parts by weight: 8-11% of free phenol, 0.6-0.7% of free aldehyde, 3-6% of water, 77-82% of solid content, 46-50% of carbon residue rate, 8000-10000mPa.s of viscosity (25 ℃) and 550-650 of molecular weight; the preparation method of the phenolic resin binder comprises the following steps: weighing the following raw materials in parts by weight: adding 35% of pure lignin, 32% of phenol, 32.5% of formaldehyde and 0.5% of sodium hydroxide into a reaction kettle; opening an emptying valve at the top end of the horizontal condenser, controlling the condensing water pressure of the condenser to be between 0.3MPa and 0.4MPa, and then opening a temperature rising switch to introduce steam into a jacket of the reaction kettle; stirring and heating up to the initial temperature of not more than 30 ℃, heating up to 80 ℃, strictly controlling the heating speed to be 1 ℃ per 1min, controlling the heating up time to be within 60-70min, heating up to 93-95 ℃, then preserving heat for 90min, cooling to 45 ℃, and discharging to obtain the phenolic resin binder.
The particle size of the electrically calcined anthracite and the artificial graphite after being mixed is as follows by weight: 0-12% of-8 +4, 10-15% of-4 +2, 14-19% of-2 +1, 7-12% of-1 +0.5, 12-17% of-0.5 +15, 8-13% of-0.15 +0.075 and 21-26% of-0.075.
The preparation method comprises the following steps:
s1, crushing, grinding and screening the carbon aggregate electrically-forged anthracite and the artificial graphite, and then mixing the materials according to the raw material proportion and the granularity composition requirement, wherein the non-carbon additive is mixed together according to the proportion requirement;
s2, adding the prepared aggregate into a powerful mixing and kneading machine (with an effective volume of 2000-3000 l, manufactured by Germany Airy corporation) for dry mixing at a high speed for 1-3 minutes, and then adding the phenolic resin binder for wet mixing for 10-15 minutes, wherein the paste does not need to be heated additionally in the mixing process, but because the mechanical energy is converted into the heat energy in the high-speed mixing process and the chemical reaction occurs in the mixing process, the temperature of the paste can rise to 40-60 ℃, and the product quality cannot be influenced;
s3, discharging the mixed paste from the powerful kneader into a disc feeder (Germany Airisch company) below the powerful kneader, and uniformly discharging the paste into a forming die below the powerful kneader through the disc feeder;
s4, performing compression molding on the paste subjected to uniform distribution in the mold on a compression molding machine (a vertical compression molding machine, the maximum pressure of the molding machine is 4000-7000 tons, the pressure applied to the upper surface of the paste in the molding process is 15-50MPa, the molding machine is provided with a simulated bidirectional pressurizing device and is used for simulating bidirectional pressurizing molding), wherein the vacuum degree of a vacuum tank is required to be more than-0.09 MPa, the vacuum degree in the working process is required to be more than-0.08 MPa, and the method comprises the following specific steps: after the material is finished, the die with the paste enters a forming station, a vacuum cover falls and is compressed, vacuumizing is started, after vacuumizing is performed for 30-60s, an upper punch of a die press moves downwards to press, pressure maintaining is performed after the pressure is uniformly increased to a target pressure, the pressure maintaining time is 30-60s, pressure relief is performed after pressing is finished, vacuum is removed, the upper punch is lifted, the die moves out of the forming station, a demolding station is reached, a carbon block is ejected to a tray, the forming process is completed, and the specification of the formed carbon block is as follows: the length is 2000-4000mm, the width is 400-700mm, and the height is 400-700 mm;
s5, after the molding procedure is finished, drying and curing the molded carbon block product and the tray together, wherein the drying and curing are as follows: after molding, the carbon block which has no strength and can not be lifted and the tray enter a drying kiln together, in the drying kiln, at the temperature of 60-80 ℃, phenolic resin in the carbon block is subjected to molecular condensation gradually, water is removed, and after drying and dehydration for 36-72 hours, although the resin is not completely cured, the carbon block has a certain strength, and can be lifted and charged; the dried carbon block in a semi-solidified state is hoisted and placed into a ring type roasting furnace for roasting, and the roasting temperature-rising system is shown in table 1:
TABLE 1
And S6, machining according to the blast furnace masonry requirements to obtain the ultramicropore carbon brick for the hearth of the blast furnace bottom.
Example 2:
raw materials: the aggregate phenolic resin adhesive comprises 100 parts of aggregate and 20 parts of phenolic resin adhesive by weight;
the aggregate comprises two parts, namely a carbonaceous aggregate and a non-carbonaceous additive, and 90 parts of the carbonaceous aggregate and 10 parts of the non-carbonaceous additive are contained in 100 parts of the aggregate by weight;
the carbonaceous aggregate comprises 90% of electrically calcined anthracite and 10% of artificial graphite by weight.
The non-carbonaceous additive comprises 30% of metal silicon powder and one or a mixture of more than two of alumina powder (alpha-Al 2O3 micro powder, white corundum powder, brown corundum powder and the like), silicon carbide powder (alpha-SiC or beta-SiC), titanium oxide powder (anatase type or rutile type) and zirconia powder, wherein the mixture of one or more than two of the alumina powder, the silicon carbide powder, the titanium oxide powder and the zirconia powder accounts for 70%, the chemical purity of the non-carbonaceous additive is more than 95% by weight, the particle size is screened by a 0.045mm (325 mesh) metric standard screen, and the part smaller than 0.045mm (325 mesh) is more than 95% by weight.
The phenolic resin binder comprises the following components in parts by weight: 8-11% of free phenol, 0.6-0.7% of free aldehyde, 3-6% of water, 77-82% of solid content, 46-50% of carbon residue rate, 8000-10000mPa.s of viscosity (25 ℃) and 550-650 of molecular weight; the preparation method of the phenolic resin binder comprises the following steps: weighing the following raw materials in parts by weight: adding 40% of pure lignin, 29% of phenol, 30.2% of formaldehyde and 0.8% of sodium hydroxide into a reaction kettle; opening an emptying valve at the top end of the horizontal condenser, controlling the condensing water pressure of the condenser to be between 0.3MPa and 0.4MPa, and then opening a temperature rising switch to introduce steam into a jacket of the reaction kettle; stirring and heating up to the initial temperature of not more than 30 ℃, heating up to 80 ℃, strictly controlling the heating speed to be 1 ℃ per 1min, controlling the heating up time to be within 60-70min, heating up to 93-95 ℃, then preserving heat for 90min, cooling to 45 ℃, and discharging to obtain the phenolic resin binder.
The particle size of the electrically calcined anthracite and the artificial graphite after being mixed is as follows by weight: 0-12% of-8 +4, 10-15% of-4 +2, 14-19% of-2 +1, 7-12% of-1 +0.5, 12-17% of-0.5 +15, 8-13% of-0.15 +0.075 and 21-26% of-0.075.
The preparation method comprises the following steps: same as in example 1.
Example 3:
raw materials: the aggregate phenolic resin adhesive comprises 100 parts of aggregate and 17 parts of phenolic resin adhesive by weight;
the aggregate comprises two parts of carbonaceous aggregate and non-carbonaceous additive, and in 100 parts of the aggregate, 81 parts of the carbonaceous aggregate and 19 parts of the non-carbonaceous additive are calculated by weight;
the carbonaceous aggregate comprises two parts, namely electrically calcined anthracite and artificial graphite, wherein the electrically calcined anthracite accounts for 79% by weight, and the artificial graphite accounts for 21% by weight.
The non-carbonaceous additive comprises 55% of metal silicon powder and one or a mixture of more than two of alumina powder (alpha-Al 2O3 micro powder, white corundum powder, brown corundum powder and the like), silicon carbide powder (alpha-SiC or beta-SiC), titanium oxide powder (anatase type or rutile type) and zirconia powder by weight, wherein the mixture of one or more than two of the alumina powder, the silicon carbide powder, the titanium oxide powder and the zirconia powder accounts for 45%, the chemical purity of the non-carbonaceous additive is more than 95% by weight, the particle size is sieved by a 0.045mm (325 mesh) metric standard sieve, and the part smaller than 0.045mm (325 mesh) is more than 95% by weight.
The phenolic resin binder comprises the following components in parts by weight: 8-11% of free phenol, 0.6-0.7% of free aldehyde, 3-6% of water, 77-82% of solid content, 46-50% of carbon residue rate, 8000-10000mPa.s of viscosity (25 ℃) and 550-650 of molecular weight; the preparation method of the phenolic resin binder comprises the following steps: weighing the following raw materials in parts by weight: adding 38% of pure lignin, 30.5% of phenol, 30.8% of formaldehyde and 0.7% of sodium hydroxide into a reaction kettle; opening an emptying valve at the top end of the horizontal condenser, controlling the condensing water pressure of the condenser to be between 0.3MPa and 0.4MPa, and then opening a temperature rising switch to introduce steam into a jacket of the reaction kettle; stirring and heating up to the initial temperature of not more than 30 ℃, heating up to 80 ℃, strictly controlling the heating speed to be 1 ℃ per 1min, controlling the heating up time to be within 60-70min, heating up to 93-95 ℃, then preserving heat for 90min, cooling to 45 ℃, and discharging to obtain the phenolic resin binder.
The particle size of the electrically calcined anthracite and the artificial graphite after being mixed is as follows by weight: 0-12% of-8 +4, 10-15% of-4 +2, 14-19% of-2 +1, 7-12% of-1 +0.5, 12-17% of-0.5 +15, 8-13% of-0.15 +0.075 and 21-26% of-0.075.
The preparation method comprises the following steps: same as in example 1.
The carbon blocks prepared by the above examples 1-3 are compared with the technical indexes of the ultra-microporous carbon bricks for the blast furnace of the industry standard YB/T4189-2009, as shown in Table 2:
TABLE 2
The data show that the key technical indexes of the ultra-microporous carbon block, namely volume density, are greatly improved compared with the industrial standard.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A carbon block for a hearth of a blast furnace bottom is characterized by comprising 100 parts of aggregate and 13-20 parts of phenolic resin binder by weight;
the aggregate comprises two parts, namely carbonaceous aggregate and non-carbonaceous additive, and the aggregate comprises 68-90 parts of carbonaceous aggregate and 10-32 parts of non-carbonaceous additive in 100 parts of aggregate by weight;
wherein the carbonaceous aggregate comprises 70-90% of electrically calcined anthracite and 10-30% of artificial graphite by weight.
2. The carbon block for the hearth and the hearth of the blast furnace as claimed in claim 1, wherein the non-carbonaceous additive comprises one or a mixture of two or more of metal silicon powder and alumina powder (α -Al2O3 fine powder, white corundum powder, brown corundum powder, etc.), silicon carbide powder (α -SiC or β -SiC), titanium oxide powder (anatase type or rutile type), zirconia powder, wherein the metal silicon powder accounts for 30-70% by weight, the one or a mixture of two or more of alumina powder, silicon carbide powder, titanium oxide powder, zirconia powder accounts for 30-70% by weight, the non-carbonaceous additive has a chemical purity of 95% or more by weight, a particle size of 0.045mm (325 mesh) is sieved by a metric standard sieve, and a part of less than 0.045mm (325 mesh) is more than 95% by weight.
3. The carbon block for the bottom hearth of the blast furnace as claimed in claim 2, wherein the phenolic resin binder comprises the following components by weight: 8-11% of free phenol, 0.6-0.7% of free aldehyde, 3-6% of water, 77-82% of solid content, 46-50% of carbon residue rate, 8000-10000mPa.s of viscosity (25 ℃) and 550-650 of molecular weight; the preparation method of the phenolic resin binder comprises the following steps: weighing the following raw materials in parts by weight: adding 35-40% of pure lignin, 29-32% of phenol, 32.5-30.2% of formaldehyde and 0.5-0.8% of sodium hydroxide into a reaction kettle; opening an emptying valve at the top end of the horizontal condenser, controlling the condensing water pressure of the condenser to be between 0.3MPa and 0.4MPa, and then opening a temperature rising switch to introduce steam into a jacket of the reaction kettle; stirring and heating up to the initial temperature of not more than 30 ℃, heating up to 80 ℃, strictly controlling the heating speed to be 1 ℃ per 1min, controlling the heating up time to be within 60-70min, heating up to 93-95 ℃, then preserving heat for 90min, cooling to 45 ℃, and discharging to obtain the phenolic resin binder.
4. The carbon block for the bottom hearth of the blast furnace according to claim 3, wherein the electrically calcined anthracite and the artificial graphite are mixed to have the following particle size by weight: 0-12% of-8 +4, 10-15% of-4 +2, 14-19% of-2 +1, 7-12% of-1 +0.5, 12-17% of-0.5 +15, 8-13% of-0.15 +0.075 and 21-26% of-0.075.
5. The method for manufacturing carbon blocks for the hearth of a blast furnace as claimed in any one of claims 1 to 4, comprising the steps of:
s1, crushing, grinding and screening the carbon aggregate electrically-forged anthracite and the artificial graphite, and then mixing the materials according to the raw material proportion and the granularity composition requirement, wherein the non-carbon additive is mixed together according to the proportion requirement;
s2, adding the prepared aggregate into a powerful mixing and kneading machine, dry-mixing at a high speed for 1-3 minutes, adding the phenolic resin binder, and wet-mixing for 10-15 minutes, wherein no additional heating is needed to be carried out on the paste in the mixing process, but because mechanical energy is converted into heat energy in the high-speed mixing process and chemical reaction occurs in the mixing process, the temperature of the paste can rise to 40-60 ℃, and the product quality cannot be influenced;
s3, discharging the mixed paste from the powerful kneader into a disc feeder below the powerful kneader, and uniformly discharging the paste into a forming die below the powerful kneader through the disc feeder;
s4, carrying out compression molding on the paste which is uniformly distributed in the mold on a compression molding machine;
s5, after the molding procedure is finished, drying and curing the molded carbon block product and the tray together;
and S6, machining according to the blast furnace masonry requirements to obtain the ultramicropore carbon brick for the hearth of the blast furnace bottom.
6. The method for manufacturing the carbon block for the hearth and the hearth of the blast furnace as claimed in claim 5, wherein the step S4 is to mold a belt vacuum extractor, the vacuum degree of the vacuum tank is required to be more than-0.09 MPa, the vacuum degree during operation is required to be more than-0.08 MPa, and the specific steps are as follows: after distributing, the die carries paste to enter a forming station, a vacuum cover falls down to be compressed, vacuumizing is started, after vacuumizing is carried out for 30-60s, an upper punch of a die press moves downwards to press, pressure maintaining is carried out after uniform pressure rise to target pressure, the pressure maintaining time is 30-60s, pressure relief is carried out after pressing is finished, vacuum is removed, the upper punch is lifted, the die moves out of the forming station to reach a demolding station, a carbon block is ejected to a tray, and the forming process is finished.
7. The method for manufacturing a carbon block for a hearth of a blast furnace according to claim 5, wherein the drying and curing in the step S5 comprises the steps of: after molding, the carbon block which has no strength and can not be lifted and the tray enter a drying kiln together, in the drying kiln, at the temperature of 60-80 ℃, phenolic resin in the carbon block gradually carries out molecular condensation, water is removed, and after drying and dehydration for 36-72 hours, although the resin in the carbon block is not completely cured, the carbon block has a certain strength, and can be lifted and charged in a furnace; and hoisting the dried carbon block in the semi-solidified state, and putting the carbon block into a ring type roasting furnace for roasting.
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| CN114988890A (en) * | 2022-05-06 | 2022-09-02 | 武汉科技大学 | Cold isostatic pressing formed ultramicropore carbon brick and preparation method thereof |
| CN115745611A (en) * | 2022-12-09 | 2023-03-07 | 上海沃骋有色金属有限公司 | Environment-friendly resin binder and application method thereof |
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