CN115159967A - High-oxidation-resistance environment-friendly iron runner castable - Google Patents
High-oxidation-resistance environment-friendly iron runner castable Download PDFInfo
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Abstract
The invention discloses a high-oxidation-resistance environment-friendly iron runner castable which comprises the following components in percentage by mass: 12-3mm of bauxite chamotte, 35-50 percent; 3-0mm and 30-45% of silicon carbide; waste electrode graphite fragments of 0.5-0mm1-3%; 0.2-1% of graphite electrode dust removal powder; 1-2% of calcium aluminate cement; 2.0 to 3.0 percent of silicon dioxide micro powder; 5.0 to 9.0 percent of alumina micro powder; 0.8-2.5% of elemental silicon powder; 0.5 to 2.0 percent of titanium boride powder; 0.10 to 0.20 percent of explosion-proof agent; 0.02-0.05% of surfactant; 0.1 to 0.15 percent of water reducing agent; the invention provides a novel scheme of a high-oxidation-resistance iron runner castable, which introduces a high-efficiency antioxidant and a novel carbon source into a material to ensure that the oxidation resistance of the material is better under a high-temperature condition, thereby improving the service performance of the material.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a high-oxidation-resistance environment-friendly iron runner castable.
Background
In the prior art, the blast furnace casting material of the iron runner of the casting house basically adopts Al 2 O 3 The SiC and C mainly play a role in improving the erosion resistance of slag, and the C is easily oxidized at high temperature to lose the erosion resistance and leave a large number of pores in the material to be further worsenedThe material properties are improved. The traditional iron runner castable generally adopts ball asphalt and carbon black as carbon sources, the ball asphalt has low carbon content, a large amount of toxic and harmful smoke is generated in the baking process of the iron runner materials, the granularity of the ball asphalt is coarse, large holes are easily formed after oxidation, and the carbon black belongs to amorphous carbon and has lower oxidation temperature compared with graphite. The oxidation resistance effect of daily used boron carbide, simple substance silicon and the like is not obvious enough, and when the castable is used at high temperature for a long time, the carbon source is usually oxidized and consumed in a short time.
CN202110210836.4 discloses an iron runner castable containing two carbon sources and a preparation method thereof, and the iron runner castable has better normal temperature and high temperature performance by adopting the composite addition of carbon black and ball asphalt, but the ball asphalt has low carbon content and high content of harmful substances, and generates toxic and harmful gases at high temperature.
CN200910242245.4 discloses a tapping channel castable with good oxidation resistance, which adopts silicon carbide fine powder, asphalt powder and metal nitride to reduce porosity and improve density and strength, but has the environmental protection problem of the asphalt powder and introduces low-melting substances into clay.
Disclosure of Invention
The invention aims to provide a scheme of a novel high-oxidation-resistance iron runner castable, which introduces a high-efficiency antioxidant and a novel carbon source into a material to ensure that the oxidation resistance of the material is better under a high-temperature condition, thereby improving the service performance of the material.
In order to achieve the purpose, the technical scheme is as follows:
the environment-friendly iron runner castable with high oxidation resistance comprises the following components in percentage by mass:
according to the scheme, the high-aluminium bauxite chamotte adopts 12-8mm,8-5mm,5-3mm is compounded with three kinds of grains, wherein Al 2 O 3 Content is more than or equal to 88wt%, fe 2 O 3 The content is less than or equal to 1.8wt percent.
According to the scheme, the silicon carbide is black silicon carbide and is prepared by compounding and matching four particle sizes of 3-1mm,1-0mm,0.088-0mm and 0.044-0 mm; the SiC content is more than or equal to 97wt percent.
According to the scheme, the waste electrode graphite scraps are cut scraps after graphite electrode processing, wherein the carbon content is more than or equal to 98wt%, and the particle size is 0.5-0mm; the graphite electrode is artificial graphite which is prepared by mixing raw materials including high-quality calcined petroleum coke, pressing and molding the raw materials and then treating the raw materials in a non-oxidizing atmosphere at 2500-3000 ℃.
According to the scheme, the graphite electrode dust removal powder is obtained by collecting dust generated in the processing process of the graphite electrode through a dust removal system, wherein the carbon content is more than or equal to 95wt%, and the granularity d50 is less than or equal to 12um.
According to the scheme, the content of the silicon dioxide micro powder is more than or equal to 96%, and the particle size d50=0.2-0.4 um.
According to the scheme, the alumina micropowder Al 2 O 3 Content 99.8%, d50=1.97um.
According to the scheme, the content of the elemental silicon powder is more than or equal to 98wt%, the granularity is 0.088-0mm and 0.044-0mm, and the mass ratio of fine powder is 1:1 is obtained by compounding.
According to the scheme, the titanium boride powder is ultrafine powder with the particle size of d50=1.5um, wherein TiB 2 The content is more than or equal to 99 percent.
According to the scheme, the explosion-proof agent is simple-substance aluminum powder with the granularity of 0.088-0mm, and the content of the simple-substance aluminum is more than or equal to 99%.
According to the scheme, the surfactant is food-grade sodium carboxymethylcellulose (CMC), the viscosity is 1500-2000, and the pH value is 6.5-8.
According to the scheme, the water reducing agent adopts a water reducing agent with the type FS20 and Wuhan Shanda. The water reducing agent is a high polymer water reducing agent synthesized on the basis of ethylene glycol, can effectively reduce the water adding amount of the casting material and improve the uniform distribution of casting material fine powder, so that the casting material is easy to stir, and the casting material formed by casting is not sticky and does not bleed.
The food-grade CMC is an organic matter which is very soluble in water, and is coated on the dust powder after being dissolved in the water, so that the hydrophilicity of the dust powder is improved.
After the crushed graphite and the electrode graphite dust-pumping powder are calcined in a high-temperature reducing atmosphere, the content of organic oil in the crushed graphite and the electrode graphite dust-pumping powder is very low, and the hydrophilicity is improved to a certain extent. And because the natural crystalline flake graphite is calcined and re-granulated, the granular form of the natural crystalline flake graphite is not flaky but granular, and can be uniformly dispersed in the castable under the combined action of the surfactant.
Because the final form is crystalline after high-temperature calcination, the oxidation temperature is greatly improved compared with amorphous carbon, the reaction activity with simple substance silicon is higher, and a large amount of silicon carbide whiskers are generated in the material. In addition, since the attack of the liquid iron slag generally starts from the matrix, the pores in the matrix and the substances that react easily with the slag are weak points against the attack of the slag. The superfine dust-pumping powder is uniformly dispersed in a casting material matrix, so that the matrix is more densified and highly carbonized, a large amount of fine carbon is contained in the matrix, the carbon is not easily wetted by iron slag, and when the iron slag liquid erodes into the matrix, the matrix containing a large amount of carbon powder erodes into the iron slag liquid to form turbid liquid with extremely high viscosity, so that the erosion speed is delayed.
The titanium boride can generate oxidation reaction with oxygen in the air at 500 ℃ to generate B 2 O 3 Titanium dioxide is filled in the pores of the casting material to improve the compactness of the casting material, B 2 O 3 The graphite powder and the graphite dust-extraction powder are matched to further enhance the oxidation resistance of the material. The titanium dioxide generated after the titanium boride is oxidized promotes the generation of mullite in the castable, and the titanium dioxide has high melting point (above 1800 ℃) with compounds formed by calcium oxide, aluminum oxide and the like due to the high melting point of the titanium dioxide, so that the titanium dioxide and the calcium oxide, the aluminum oxide and the like promote the generation of mulliteWhen the high-temperature slag erodes and erodes the iron runner castable, titanium dioxide in the castable is mixed with slag liquid, the viscosity of the high-temperature slag is increased, so that the slag is not easy to permeate into the castable and is adhered and crystallized on the surface of the castable to form a high-melting-point protective layer, thereby relieving the erosion speed of the slag on the castable and improving the slag erosion resistance of the material.
Under the condition of high temperature, a large amount of fine elemental silicon powder reacts to generate a large amount of SiO (g), the SiO (g) diffuses to the surface of the material, and the SiO (g) is further oxidized to generate SiO 2 (s) blocking pores, forming a layer of dense layer on the surface of the material, and improving the oxidation resistance of the material. The slightly thicker elemental silicon powder has smaller surface area and slower oxidation, so that the antioxidant effect can be continuously provided in the long-term use process of the castable, and the generated silicon dioxide is coated on the surface of the elemental silicon powder, so that the contact area of the elemental silicon powder and oxygen is reduced, and the oxidation is slower, so that the existence of the elemental silicon can still be observed in the cast material sample decarburized layer after being sintered at 1400 ℃. During the tapping process, when high-temperature slag erodes the decarburized layer, simple substance silicon particles and generated SiO 2 The silicon content in the slag is also increased, so that the CaO/SiO content in the slag is increased 2 The ratio is further reduced, the calcium-silicon ratio is reduced, the alkalinity of the slag can be effectively reduced, and the lower the alkalinity is, the higher the viscosity of the slag is. Besides improving the oxidation resistance, the simple substance silicon reacts with the graphite fragments and the graphite dust removal powder in the material to form a large amount of silicon carbide whiskers. The graphite fragments and the graphite dust removal powder are crystalline structures, and researches show that the graphite surface of the crystalline structure has higher activation energy and is easier to react with elemental silicon to generate silicon carbide whiskers, so that the high-temperature strength of the material is improved.
Compared with the prior art, the invention has the beneficial effects that:
the iron runner castable provided by the invention does not adopt ball asphalt which has low carbon content and releases a large amount of harmful gas, and adopts dust-pumping powder collected by an electrode graphite crushing and dust removing system generated by processing a graphite electrode, so that the problem of secondary recycling of carbon resources is solved, and the high-temperature oxidation resistance in the castable is improved.
Titanium boride ultrafine powder with good oxidation resistance is added, the titanium boride ultrafine powder is oxidized at a lower temperature to generate titanium dioxide with a high melting point and liquid-phase boron oxide, the oxidation thickness of the iron runner castable material added with the titanium boride is thinner than that of the iron runner castable material without the titanium boride at 800 ℃, the oxidation resistance of the titanium boride reaches a peak value at 1100 ℃, the section of the castable material is completely black, and the oxidation resistance effect is very obvious. The generated titanium dioxide with high melting point can better fill the air holes of the casting material, so that the casting material is tightly stacked, the microstructure of the casting material is improved, a large amount of titanium dioxide is not easy to react with high-temperature slag to generate low-melting matters, and when the high-temperature slag is contacted with the matrix of the casting material containing the titanium dioxide, the titanium dioxide is corroded by the slag and is mixed into the blast furnace slag, the viscosity of the blast furnace slag can be greatly increased due to the high melting point, the permeation speed of the blast furnace slag is reduced, the slag with high viscosity is adhered to the wall of the groove, a barrier is provided for the direct contact of the blast furnace slag and the iron runner casting material, and the damage speed of the casting material is slowed down.
The iron runner castable provided by the invention adopts two elemental silicon powders with different granularities, so that the problem that the elemental silicon powders with single granularity react too violently to generate SiO is solved 2 The large amount of the silicon powder causes the problem of overlarge volume expansion, and the simple substance silicon powder with two granularities ensures that the castable continuously provides oxidation resistance protection and continuously improves the strength of the castable in the long-term use process.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention, but should not be construed as limiting the scope of the invention.
The indexes of the raw materials used in the specific implementation mode are as follows:
the high-alumina bauxite clinker is compounded and matched by three granularities of 12-8mm,8-5mm and 5-3mm, and the matching mass ratio is 20:20:5. the main components of the composition are respectively as follows: al (Al) 2 O 3 ：88.21％，SiO 2 ：6.50％，Fe 2 O 3 ：1.64％。
The silicon carbide is black silicon carbide which is compounded and matched by adopting four granularities of 3-1mm,1-0mm,0.088-0mm and 0.044-0mm, and the matching mass ratio is 11:14:12. the SiC content was 97.8%.
The average particle size of the silicon dioxide micro powder is 0.23um, and the content of the silicon dioxide is 96.3 percent.
The particle size of the electrode graphite is 0.5-0mm, and the content of C is 98.2%. The particle size of the electrode graphite dust powder is d50=12.6um, and the C content is 96.7%. The crushed graphite and the graphite dust powder are both from Henan Hexiong graphite Co.
Calcium aluminate cement Al 2 O 3 The content was 69.63% and the CaO content was 29.68%.
Alumina micropowder seed Al 2 O 3 Content 99.8%, d50=1.97um.
The content of titanium boride in the titanium boride micro powder is more than or equal to 99 percent, and d50=1um.
The elemental silicon powder adopts two particle sizes of 0.088-0mm and 0.044-0mm, and the matching proportion is 1:1.
the granularity of the explosion-proof agent powder is 0.088-0.074mm, and the content of the simple substance aluminum is more than or equal to 99 percent.
Water reducing agent manufacturers: wuhan Shangda, model FS20.
Example 1
The iron runner castable comprises the following components in percentage by weight:
example 2
The iron runner castable comprises the following components in percentage by weight:
example 3
The iron runner castable comprises the following components in percentage by weight:
comparative example 1
The iron runner castable comprises the following components in percentage by weight:
comparative example 2
The iron runner castable comprises the following components in percentage by weight:
the samples prepared according to the above examples and comparative examples were dried at 110 ℃ 1241, subjected to a slag erosion resistance test and a thermal fracture resistance test, and the oxidation thickness and strength after heat treatment at different temperature points were measured. Slag resistance experiment the slag sample was fired at 800 ℃ 131, the channel slag was loaded into the crucible sample, and the 1520 ℃ 131 slag resistance experiment was performed. The performance index test of the iron runner castable obtained in the examples 1-3 and the comparative example is shown in the table 1.
TABLE 1
Table 1 shows that the iron runner castable provided in examples 1 to 3 of the present invention uses the scrap material generated during the processing of the graphite electrode and the dust-removing powder collected by the dust-removing system as a carbon source, and further improves the hydrophilicity by using a surfactant, and has a high content of graphite carbon scrap and an oxidation resistance temperature higher than those of pitch pellets and carbon black. Because the graphitization degree is high, the material can be more easily combined with simple substance silicon, simple substance aluminum and the like to generate silicon carbide and aluminum carbide whiskers in a high-temperature reducing atmosphere, so that the material is more densified at high temperature and has higher strength.
The iron runner castable added with the antioxidant titanium boride and the elementary silicon with different particle sizes is obviously thinned after being respectively sintered at 800 ℃ 131 and 1100 ℃ 131, particularly, the section of a sample after being sintered at 1100 ℃ 131 and 241 is basically completely black, and the residual carbon content of the sample after being sintered at 1100 ℃ 1241 is basically 0.8-1.1% through detection. And the section of the sample is completely whitened after the iron runner castable which is not added with the antioxidant is sintered at 1100 ℃ and 1241, the content of carbon residue detected by the sample is very low, and the improvement effect of the two antioxidants on the oxidation resistance of the material is fully demonstrated. The examination of the 1500 ℃ 131. DegreeCin the sample also revealed that the apparent porosity of the example was lower and the sample was denser. In the embodiment, the antioxidant plays a good role in antioxidation, so that the carbon content in the material is always kept at a higher level, the strength of the material is improved, the apparent porosity of the material is reduced, and the slag scouring corrosion resistance of the sample is improved.
Claims (10)
1. The high-oxidation-resistance environment-friendly iron runner castable is characterized by comprising the following components in percentage by mass:
2. the environment-friendly type iron runner castable with high oxidation resistance as claimed in claim 1, wherein the high bauxite chamotte is compounded and matched by three granularities of 12-8mm,8-5mm and 5-3mm, wherein Al is 2 O 3 Content is more than or equal to 88wt%, fe 2 O 3 The content is less than or equal to 1.8wt percent.
3. The environment-friendly high-oxidation-resistance iron runner castable as claimed in claim 1, wherein the silicon carbide is black silicon carbide, and is prepared by compounding and matching four kinds of granularity of 3-1mm,1-0mm,0.088-0mm and 0.044-0 mm; the SiC content is more than or equal to 97wt percent.
4. The environment-friendly iron runner castable with high oxidation resistance as claimed in claim 1, wherein the waste electrode graphite scraps are cut scraps after graphite electrode processing, wherein the carbon content is not less than 98wt%, and the particle size is 0.5-0mm; the graphite electrode is artificial graphite which is prepared by mixing raw materials including high-quality calcined petroleum coke, pressing and molding the raw materials and then treating the mixture in a non-oxidizing atmosphere at the temperature of 2500-3000 ℃.
5. The environment-friendly high-oxidation-resistance iron runner castable material as claimed in claim 1, wherein the graphite electrode dusting powder is obtained by collecting dust generated in the processing process of a graphite electrode through a dusting system, wherein the carbon content is more than or equal to 95wt%, and the particle size d50 is less than or equal to 12um.
6. The environment-friendly type iron runner castable material with high oxidation resistance as claimed in claim 1, wherein the content of the silicon dioxide micropowder is not less than 96%, and the superfine micropowder with the particle size d50=0.2-0.4 um; the alumina micro powder Al 2 O 3 Content 99.8%, d50=1.97um.
7. The environment-friendly high-oxidation-resistance iron runner castable as claimed in claim 1, wherein the elemental silicon powder contains not less than 98wt% of elemental silicon, and the particle size of the elemental silicon powder is 0.088-0mm and 0.044-0mm fine powder according to the mass ratio of 1:1 is obtained by compounding.
8. The environment-friendly iron runner castable material with high oxidation resistance as claimed in claim 1, wherein the titanium boride powder is ultrafine powder with the particle size d50=1.5um, wherein TiB 2 The content is more than or equal to 99 percent.
9. The environment-friendly type iron runner castable material with high oxidation resistance as claimed in claim 1, wherein the explosion-proof agent is elemental aluminum powder with the granularity of 0.088-0mm, and the content of elemental aluminum is more than or equal to 99%; the water reducing agent adopts a water reducing agent of Wuhan Shanda, model FS20.
10. The environment-friendly type iron runner castable material with high oxidation resistance as claimed in claim 1, wherein the surfactant is food grade sodium carboxymethyl cellulose, the viscosity is between 1500-2000, and the pH value is between 6.5-8.
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| CN202210877281.3A CN115159967A (en) | 2022-07-25 | 2022-07-25 | High-oxidation-resistance environment-friendly iron runner castable |
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| CN202210877281.3A CN115159967A (en) | 2022-07-25 | 2022-07-25 | High-oxidation-resistance environment-friendly iron runner castable |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02172860A (en) * | 1988-12-26 | 1990-07-04 | Toshiba Ceramics Co Ltd | Nozzle for casting |
| US5185300A (en) * | 1991-03-11 | 1993-02-09 | Vesuvius Crucible Company | Erosion, thermal shock and oxidation resistant refractory compositions |
| CN1214326A (en) * | 1998-09-28 | 1999-04-21 | 宝山钢铁(集团)公司 | Ultra-low cement deposit material for tap hole of iron-mixing bogie |
| CN102633513A (en) * | 2012-05-08 | 2012-08-15 | 中国钢研科技集团有限公司 | Fast-baking explosion proof type refractory castable for blast furnace iron runner |
| CN111574206A (en) * | 2020-05-12 | 2020-08-25 | 唐山市国亮特殊耐火材料有限公司 | Anti-corrosion iron runner castable for large blast furnace |
-
2022
- 2022-07-25 CN CN202210877281.3A patent/CN115159967A/en active Pending
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|---|---|---|---|---|
| JPH02172860A (en) * | 1988-12-26 | 1990-07-04 | Toshiba Ceramics Co Ltd | Nozzle for casting |
| US5185300A (en) * | 1991-03-11 | 1993-02-09 | Vesuvius Crucible Company | Erosion, thermal shock and oxidation resistant refractory compositions |
| CN1214326A (en) * | 1998-09-28 | 1999-04-21 | 宝山钢铁(集团)公司 | Ultra-low cement deposit material for tap hole of iron-mixing bogie |
| CN102633513A (en) * | 2012-05-08 | 2012-08-15 | 中国钢研科技集团有限公司 | Fast-baking explosion proof type refractory castable for blast furnace iron runner |
| CN111574206A (en) * | 2020-05-12 | 2020-08-25 | 唐山市国亮特殊耐火材料有限公司 | Anti-corrosion iron runner castable for large blast furnace |
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| 钟香崇等编著: "《电热法制取铝硅合金》", vol. 1, 湖北科学技术出版社, pages: 400 - 379 * |
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