CN111943653A - Environment-friendly anhydrous stemming for blast furnace taphole and preparation method thereof - Google Patents

Environment-friendly anhydrous stemming for blast furnace taphole and preparation method thereof Download PDF

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CN111943653A
CN111943653A CN202010624180.6A CN202010624180A CN111943653A CN 111943653 A CN111943653 A CN 111943653A CN 202010624180 A CN202010624180 A CN 202010624180A CN 111943653 A CN111943653 A CN 111943653A
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environment
mass
blast furnace
parts
furnace taphole
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CN111943653B (en
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金金
夏扬
佘顺峰
魏军魁
佘云锋
周诒慧
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Changxing Furnace Material Co ltd
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Abstract

The invention relates to an environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The technical scheme is as follows: the method comprises the following steps of taking 25-35 parts by mass of brown fused alumina, 20-35 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.5-2 parts by mass of kaolin micropowder as raw materials, taking polycarbosilane or polysilazane accounting for 10-25 wt% of the raw materials as a bonding agent, and taking 0.2-2 wt% of carboxymethyl cellulose and citric acid as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole. The invention forms SiC or Si by spherical modification of coke and in-situ reaction sintering of a binder3N4NetworkThe prepared environment-friendly anhydrous stemming for the blast furnace taphole has the characteristics of excellent molten iron scouring resistance and erosion resistance, easy sintering, high medium-high temperature strength, strong plasticity, simple process and environmental friendliness.

Description

Environment-friendly anhydrous stemming for blast furnace taphole and preparation method thereof
Technical Field
The invention belongs to the technical field of refractory materials for blast furnace tapholes, and particularly relates to an environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof.
Background
With the rapid development of smelting technology, large-scale blast furnaces and high-strength smelting become the mainstream of the current ferrous metallurgy field, which provides a new challenge for stemming for blast furnace tapholes. Generally, the stemming is a refractory plastic material for plugging a blast furnace taphole, is the most serious area for erosion and scouring of iron slag, and has great influence on the service life of the blast furnace. In the blast furnace ironmaking process, a taphole needs to be repeatedly filled and opened, and stemming needs to bear strong physical and chemical erosion of blast furnace molten iron and slag liquid. Therefore, the stemming needs to have higher refractoriness, slag resistance and molten iron scouring resistance; in addition, the stemming also needs to have high volume stability, better sintering performance, high medium-high temperature strength and certain opening performance.
At present, anhydrous stemming is generally used at a blast furnace taphole, tar and coal tar are used as binding agents, and a carbon network structure is formed by carbonizing the binding agents to combine aggregate and matrix. However, tar and coal pitch generally contain a large amount of hydrocarbons of polycyclic aromatic hydrocarbons, of which benzopyrene (BaP) is the most typical having strong carcinogenicity. In order to solve the environmental protection problem, the patent technology of 'an environmental protection type stemming for a blast furnace' (CN104725063A) discloses an environmental protection type stemming which takes carbon resin and phenolic resin as bonding agents to replace tar and asphalt. Although the stemming prepared by the method solves the problem of formation of carcinogenic flue gas in the stemming and improves the operation environment in front of a furnace, the porosity of the stemming is obviously increased due to low residual carbon content of the phenolic resin, and the molten iron scouring resistance of the stemming is obviously reduced. In order to improve the molten iron scouring resistance of the stemming, the patent technology of a dry-type low-carbon environment-friendly stemming and a manufacturing method thereof (CN 104478443A) discloses an environment-friendly stemming prepared by adding a composite raw material of silicon carbide and silicon nitride, and improves the erosion resistance and the scouring resistance of the stemming. When a large amount of silicon carbide and silicon nitride are added and a network structure is formed in the stemming, the erosion resistance and corrosion resistance of the stemming are obviously improved; however, silicon carbide and silicon nitride are both compounds combined by non-metallic bonds, and the great addition of the silicon carbide and the silicon nitride in the stemming inevitably causes the stemming to be difficult to sinter and the high-temperature strength to be sharply reduced; therefore, when the stemming is prepared by the patent technology, the addition amount of silicon carbide and silicon nitride must be controlled in a certain range, so that the improvement range of the erosion resistance of the stemming is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide the preparation method of the environment-friendly anhydrous stemming for the blast furnace taphole, which has simple process, has the advantages of excellent molten iron scouring resistance and corrosion resistance, easy sintering, high medium-high temperature strength, no environmental pollution, easy field production and the like, and can meet the requirement of the service environment of the taphole in the large-scale high-strength smelting process of the blast furnace.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the method comprises the following steps of taking 25-35 parts by mass of brown fused alumina, 20-35 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.5-2 parts by mass of kaolin micropowder as raw materials, taking polycarbosilane or polysilazane accounting for 10-25 wt% of the raw materials as a bonding agent, and taking 0.2-2 wt% of carboxymethyl cellulose and citric acid as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-60 parts by mass, 30-40 parts by mass and 10-20 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
Al of the brown corundum2O3The content is more than or equal to 95 wt%; the grain composition of the brown corundum is as follows: the brown corundum with the grain diameter of 1-3 mm accounts for 45-50 wt% of the brown corundum, the brown corundum with the grain diameter of less than 1mm accounts for 25-30 wt% of the brown corundum, and the brown corundum with the grain diameter of less than 1mm accounts for 25-30 wt% of the brown corundum.
The carbon content in the crystalline flake graphite is more than or equal to 95 wt%, and the granularity is less than or equal to 0.074 mm.
The molecular weight of the polycarbosilane is more than or equal to 1800, and the polysilazane concentration is more than or equal to 58 wt%.
Al in the andalusite powder2O3The content is more than or equal to 60 wt%, and the granularity is less than or equal to 0.074 mm; the residual carbon rate of the phenolic resin powder is more than or equal to 40 wt%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
the invention adopts polycarbosilane or polysilazane as a bonding agent to prepare the environment-friendly anhydrous stemming to replace the traditional tar, coal tar, phenolic resin and the like. On one hand, the polycarbosilane or polysilazane is fully utilized to react in situ at high temperature to form SiC or Si3N4The high-temperature sintering of the stemming is realized at the same time of the network, and SiC or Si is formed in situ3N4The network reinforces and toughens the stemming and SiC or Si3N4The stemming is non-wetting to molten iron and slag liquid, has excellent molten iron scouring resistance and erosion resistance, and prolongs the service life of the taphole stemming; on the other hand, the environment-friendly anhydrous stemming is prepared by adopting polycarbosilane or polysilazane as a bonding agent, the process is simple, no toxic smoke is generated during pyrolysis, and the harm of the stemming to the environment and the human body is avoided, so that the prepared environment-friendly anhydrous stemming for the blast furnace taphole is green and environment-friendly.
Spherical modified coke is introduced into the environment-friendly anhydrous stemming prepared by the invention, the flowability and plasticity of particles in the stemming are improved through the spherical modified coke, and the Marshall value of the stemming is reduced; furthermore, the spherical modified coke also comprises andalusite powder and phenolic resin powder, wherein the phenolic resin can be carbonized at high temperature to form glassy carbon, and reacts with the andalusite in situ to form SiC and Al2O3To achieve the purpose of reaction sinteringMeanwhile, SiC is formed in situ to improve the molten iron scouring resistance of the stemming. In addition, certain volume expansion effect exists in the process that the unreacted andalusite is subjected to primary mullite and secondary mullite at high temperature, and the volume stability of the stemming at high temperature can be improved.
Flake graphite is added into the environment-friendly anhydrous stemming prepared by the invention, and the flake graphite plays a role in lubricating the stemming, so that the plasticity of the stemming can be improved, and the Marshall value of the stemming is reduced; in addition, the scale graphite reacts with andalusite at high temperature to form SiC in situ, which is beneficial to the high-temperature strength and the molten iron scouring resistance of the stemming. The non-wetting property of the scale graphite and the molten iron can improve the anti-corrosion performance of the stemming and prevent the reaming of the taphole.
The environment-friendly anhydrous stemming for the blast furnace taphole prepared by the invention is detected as follows: the volume density of the powder is 1.87 to 1.97g/cm at 200 ℃ for 24h3The volume density is 1.80-1.95 g/cm at 1400 ℃ for 3h3(ii) a The bending strength at 200 ℃ is 7-10 MPa for 24h, the bending strength at 1400 ℃ is 7-12 MPa for 3h, the Marshall value (40 ℃) is 0.4-1.0 MPa, the average tapping time is 166-200 min/time, and the average tapping amount per time is 1005-1258 tons/time.
Therefore, the invention has the characteristics of simple process and environmental protection, and the prepared environment-friendly anhydrous stemming for the blast furnace taphole has excellent molten iron scouring capability and corrosion resistance, easy sintering, high medium-high temperature strength and strong plasticity.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope.
Al of the brown corundum2O3The content is more than or equal to 95 wt%; the grain composition of the brown corundum is as follows: the brown corundum with the grain diameter of 1-3 mm accounts for 45-50 wt% of the brown corundum, the brown corundum with the grain diameter of less than 1mm accounts for 25-30 wt% of the brown corundum, and the brown corundum with the grain diameter of less than 1mm accounts for 25-30 wt% of the brown corundum.
The carbon content in the crystalline flake graphite is more than or equal to 95 wt%, and the granularity is less than or equal to 0.074 mm.
The molecular weight of the polycarbosilane is more than or equal to 1800, and the polysilazane concentration is more than or equal to 58 wt%.
Al in the andalusite powder2O3The content is more than or equal to 60 wt%, and the granularity is less than or equal to 0.074 mm; the residual carbon rate of the phenolic resin powder is more than or equal to 40 wt%.
Example 1
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
firstly, 25-30 parts by mass of brown fused alumina, 30-35 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.5-2 parts by mass of kaolin micropowder are used as raw materials, polycarbosilane accounting for 20-25 wt% of the raw materials is used as a bonding agent, and carboxymethyl cellulose and citric acid accounting for 0.5-2 wt% of the raw materials are used as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-55 parts by mass, 34-40 parts by mass and 10-18 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in the embodiment 1 is detected: the volume density of the powder is 1.87 to 1.90g/cm at 200 ℃ for 24h3The volume density is 1.80-1.88 g/cm at 1400 ℃ for 3h3(ii) a The bending strength of the steel is 7-8 MPa at 200 ℃ for 24h, the bending strength of the steel is 8-11 MPa at 1400 ℃ for 3h, the Marshall value (40 ℃) is 0.4-0.8 MPa, the average tapping time is 166-189 min/time, and the average tapping quantity of each time is 1107-1256 tons/time.
Example 2
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
firstly, 30-35 parts by mass of brown fused alumina, 24-32 parts by mass of modified coke, 0.5-1 part by mass of crystalline flake graphite and 0.5-2 parts by mass of kaolin micropowder are used as raw materials, polycarbosilane accounting for 10-18 wt% of the raw materials is used as a bonding agent, and 0.2-1 wt% of carboxymethyl cellulose and citric acid are used as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of coke, andalusite powder and phenolic resin powder in the modified coke is 53-60 parts by mass, 30-35 parts by mass and 12-20 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in the embodiment 2 is detected: the volume density of the powder is 1.87 to 1.92g/cm at 200 ℃ for 24h3The volume density is 1.85-1.90 g/cm at 1400 ℃ for 3h3(ii) a The bending strength of 24 hours at 200 ℃ is 7-9 MPa, the bending strength of 3 hours at 1400 ℃ is 8-12 MPa, the Marshall value (40 ℃) is 0.5-0.9 MPa, the average tapping time is 168-195 min/time, and the average tapping amount per time is 1005-1158 tons/time.
Example 3
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
firstly, 25-32 parts by mass of brown fused alumina, 20-26 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.8-1.3 parts by mass of kaolin micropowder are used as raw materials, polycarbosilane accounting for 15-20 wt% of the raw materials is used as a bonding agent, and carboxymethyl cellulose and citric acid accounting for 0.2-1.6 wt% of the raw materials are used as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-55 parts by mass, 30-35 parts by mass and 10-18 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in the embodiment 3 is detected: the volume density of the powder is 1.89-1.91 g/cm at 200 ℃ for 24h3The volume density is 1.87-1.91 g/cm at 1400 ℃ for 3h3(ii) a The breaking strength of 24h at 200 ℃ is 8-10 MPa, the breaking strength of 3h at 1400 ℃ is 8-12 MPa, the Marshall value (40 ℃) is 0.6-1.0 MPa, the average tapping time is 172-196 min/time, and the average tapping amount per time is 1117-1258 tons/time.
Example 4
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
firstly, 25-32 parts by mass of brown fused alumina, 20-26 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 1-2 parts by mass of kaolin micropowder are used as raw materials, polysilazane accounting for 20-25 wt% of the raw materials is used as a bonding agent, and 0.6-2 wt% of carboxymethyl cellulose and citric acid are used as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-55 parts by mass, 30-35 parts by mass and 10-18 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in the embodiment 4 is detected: the volume density of the powder is 1.88 to 1.93g/cm at 200 ℃ for 24h3The volume density is 1.88 to 1.93g/cm at 1400 ℃ for 3h3(ii) a The breaking strength of 24h at 200 ℃ is 8-10 MPa, the breaking strength of 3h at 1400 ℃ is 7-11 MPa, the Marshall value (40 ℃) is 0.5-0.9 MPa, the average tapping time is 176-199 min/time, and the average tapping amount per time is 1105-1200 tons/time.
Example 5
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
firstly, 25-32 parts by mass of brown fused alumina, 20-26 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.8-1.3 parts by mass of kaolin micropowder are used as raw materials, polysilazane accounting for 10-18 wt% of the raw materials is used as a bonding agent, and 0.5-2 wt% of carboxymethyl cellulose and citric acid are used as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-55 parts by mass, 30-35 parts by mass and 10-18 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in the embodiment 5 is detected: the volume density of the powder is 1.89-1.97 g/cm at 200 ℃ for 24h3The volume density of 1400 ℃ multiplied by 3h is 1.83-1.91 g/cm3(ii) a The flexural strength of the steel is 8-10 MPa at 200 ℃ for 24h, 7-12 MPa at 1400 ℃ for 3h, and 0.4-0.9 MPa at Marshall value (40 ℃), with average tensile strengthThe iron time is 180-200 min/time, and the average iron yield per time is 1009-1255 tons/time.
Example 6
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
firstly, 25-32 parts by mass of brown fused alumina, 20-26 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.8-1.3 parts by mass of kaolin micropowder are used as raw materials, polysilazane accounting for 15-20 wt% of the raw materials is used as a bonding agent, and 0.2-1.2 wt% of carboxymethyl cellulose and citric acid are used as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of coke, andalusite powder and phenolic resin powder in the modified coke is 53-60 parts by mass, 34-40 parts by mass and 12-20 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in the embodiment 6 is detected: the volume density of the powder is 1.90-1.96 g/cm at 200 ℃ for 24h3The volume density is 1.85-1.93 g/cm at 1400 ℃ multiplied by 3h3(ii) a The breaking strength at 200 ℃ is 7-9 MPa for 24h, the breaking strength at 1400 ℃ is 8-10 MPa for 3h, the Marshall value (40 ℃) is 0.5-1.0 MPa, the average tapping time is 166-192 min/time, and the average tapping amount per time is 1012-1258 tons/time.
Example 7
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
the method comprises the following steps of firstly, taking 30-35 parts by mass of brown fused alumina, 24-32 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.5-1 part by mass of kaolin micropowder as raw materials, taking polycarbosilane and polysilazane which account for 5-12 wt% of the raw materials as bonding agents, and taking 0.4-1.8 wt% of carboxymethyl cellulose and citric acid as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-55 parts by mass, 30-35 parts by mass and 10-18 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in this example 7 was detected: the volume density of the powder is 1.92-1.97 g/cm at 200 ℃ multiplied by 24h3The volume density of 1400 ℃ multiplied by 3h is 1.86-1.95 g/cm3(ii) a The breaking strength of 24h at 200 ℃ is 8-10 MPa, the breaking strength of 3h at 1400 ℃ is 8-10 MPa, the Marshall value (40 ℃) is 0.4-0.8 MPa, the average tapping time is 176-198 min/time, and the average tapping quantity per time is 1107-1258 tons/time.
Example 8
An environment-friendly anhydrous stemming for a blast furnace taphole and a preparation method thereof. The preparation method of the embodiment comprises the following specific steps:
the method comprises the following steps of firstly, taking 30-35 parts by mass of brown fused alumina, 24-32 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.5-1 part by mass of kaolin micropowder as raw materials, taking polycarbosilane and polysilazane which account for 5-12 wt% of the raw materials as bonding agents, and taking 0.2-1.2 wt% of carboxymethyl cellulose and citric acid as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
The modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-60 parts by mass, 30-40 parts by mass and 10-20 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared in this example 8 was detected: the volume density of the powder is 1.87 to 1.95g/cm at 200 ℃ for 24h3The volume density is 1.82-1.93 g/cm at 1400 ℃ for 3h3(ii) a The breaking strength of 24h at 200 ℃ is 7-10 MPa, the breaking strength of 3h at 1400 ℃ is 7-11 MPa, the Marshall value (40 ℃) is 0.5-1.0 MPa, the average tapping time is 176-190 min/time, and the average tapping amount per time is 1065-1258 tons/time.
Compared with the prior art, the specific implementation mode has the following positive effects:
the specific implementation mode adopts polycarbosilane or polysilazane as a bonding agent to prepare the environment-friendly anhydrous stemming to replace the traditional tar, coal tar, phenolic resin and the like. On one hand, the polycarbosilane or polysilazane is fully utilized to react in situ at high temperature to form SiC or Si3N4The high-temperature sintering of the stemming is realized at the same time of the network, and SiC or Si is formed in situ3N4The network reinforces and toughens the stemming and SiC or Si3N4The stemming is non-wetting to molten iron and slag liquid, has excellent molten iron scouring resistance and erosion resistance, and prolongs the service life of the taphole stemming; on the other hand, the environment-friendly anhydrous stemming is prepared by adopting polycarbosilane or polysilazane as a bonding agent, the process is simple, no toxic smoke is generated during pyrolysis, and the harm of the stemming to the environment and the human body is avoided, so that the prepared environment-friendly anhydrous stemming for the blast furnace taphole is green and environment-friendly.
Spherical modified coke is introduced into the environment-friendly anhydrous stemming prepared by the specific embodiment, and the fluidity and plasticity of the stemming are improved through the spherical modified cokeThe Marshall value of the stemming is reduced; furthermore, the spherical modified coke also comprises andalusite powder and phenolic resin powder, wherein the phenolic resin can be carbonized at high temperature to form glassy carbon, and reacts with the andalusite in situ to form SiC and Al2O3And the aim of reaction sintering is achieved, and meanwhile, SiC is formed in situ to improve the molten iron scouring resistance of the stemming. In addition, certain volume expansion effect exists in the process that the unreacted andalusite is subjected to primary mullite and secondary mullite at high temperature, and the volume stability of the stemming at high temperature can be improved.
The environment-friendly anhydrous stemming prepared by the specific embodiment is also added with flake graphite, and the flake graphite plays a role in lubricating the stemming, so that the plasticity of the stemming can be improved, and the Marshall value of the stemming is reduced; in addition, the scale graphite reacts with andalusite at high temperature to form SiC in situ, which is beneficial to the high-temperature strength and the molten iron scouring resistance of the stemming. The non-wetting property of the scale graphite and the molten iron can improve the anti-corrosion performance of the stemming and prevent the reaming of the taphole.
The environment-friendly anhydrous stemming for a blast furnace taphole prepared by the specific embodiment is detected: the volume density of the powder is 1.87 to 1.97g/cm at 200 ℃ for 24h3The volume density is 1.80-1.95 g/cm at 1400 ℃ for 3h3(ii) a The bending strength at 200 ℃ is 7-10 MPa for 24h, the bending strength at 1400 ℃ is 7-12 MPa for 3h, the Marshall value (40 ℃) is 0.4-1.0 MPa, the average tapping time is 166-200 min/time, and the average tapping amount per time is 1005-1258 tons/time.
Therefore, the specific implementation mode has the characteristics of simple process and environmental protection, and the prepared environment-friendly anhydrous stemming for the blast furnace taphole has excellent molten iron scouring capability and corrosion resistance, is easy to sinter, and has high medium-high temperature strength and strong plasticity.

Claims (7)

1. A preparation method of environment-friendly anhydrous stemming for a blast furnace taphole is characterized by comprising the following steps: the method comprises the following steps of taking 25-35 parts by mass of brown fused alumina, 20-35 parts by mass of modified coke, 1-2 parts by mass of crystalline flake graphite and 0.5-2 parts by mass of kaolin micropowder as raw materials, taking polycarbosilane or polysilazane accounting for 10-25 wt% of the raw materials as a bonding agent, and taking 0.2-2 wt% of carboxymethyl cellulose and citric acid as additives. The raw materials, the binding agent and the additive are wet-ground for 20-30 minutes and then extruded and formed by a mud extruder to prepare the environment-friendly anhydrous stemming for the blast furnace taphole.
2. The method for preparing the environment-friendly anhydrous stemming for a blast furnace taphole according to claim 1, characterized in that: the modified coke is prepared by the following method: mixing and co-grinding coke, andalusite powder and phenolic resin powder to obtain composite powder with the granularity of less than 0.074mm, and then spraying industrial alcohol on the composite powder in a granulator to prepare spherical modified coke with the granularity of 0.1-3 mm; and finally, drying the spherical modified coke for 12-24 hours at 100 ℃ to obtain the modified coke. The mass ratio of the coke, the andalusite powder and the phenolic resin powder in the modified coke is 50-60 parts by mass, 30-40 parts by mass and 10-20 parts by mass, and the industrial alcohol accounts for 2-5 wt% of the composite powder.
3. The method for preparing the environment-friendly anhydrous stemming for a blast furnace taphole according to claim 1, characterized in that: al of the brown corundum2O3The content is more than or equal to 95 wt%; the grain composition of the brown corundum is as follows: the brown corundum with the grain diameter of 1-3 mm accounts for 45-50 wt% of the brown corundum, the brown corundum with the grain diameter of less than 1mm accounts for 25-30 wt% of the brown corundum, and the brown corundum with the grain diameter of less than 1mm accounts for 25-30 wt% of the brown corundum.
4. The method for preparing the environment-friendly anhydrous stemming for a blast furnace taphole according to claim 1, characterized in that: the carbon content in the crystalline flake graphite is more than or equal to 95 wt%, and the granularity is less than or equal to 0.074 mm.
5. The method for preparing the environment-friendly anhydrous stemming for a blast furnace taphole according to claim 1, characterized in that: the molecular weight of the polycarbosilane is more than or equal to 1800, and the polysilazane concentration is more than or equal to 58 wt%.
6. The method for preparing the environment-friendly anhydrous stemming for a blast furnace taphole according to claim 2, characterized in that: said redAl in spar powder2O3The content is more than or equal to 60 wt%, and the granularity is less than or equal to 0.074 mm; the residual carbon rate of the phenolic resin powder is more than or equal to 40 wt%.
7. The utility model provides an anhydrous stemming of environment-friendly for blast furnace taphole which characterized in that: the environment-friendly anhydrous stemming for a blast furnace taphole is prepared by the preparation method of the environment-friendly anhydrous stemming for a blast furnace taphole according to any one of claims 1 to 6.
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