CN114620997B - Method for improving performance of low-carbon magnesia carbon brick - Google Patents
Method for improving performance of low-carbon magnesia carbon brick Download PDFInfo
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Abstract
The invention discloses a method for improving the performance of a low-carbon magnesia carbon brick, which comprises the steps of adding composite fine powder into a low-carbon magnesia carbon brick matrix raw material with the carbon content of 2-6 wt%, wherein a bonding agent in the low-carbon magnesia carbon brick matrix raw material is liquid resin, and 8-15 wt% of boron/copper oxide is added into the liquid resin; the dosage of the composite fine powder is 1 to 3 weight percent of the sum of the low-carbon magnesia carbon brick matrix raw material and the composite fine powder. According to the invention, the composite fine powder and boron/copper oxide are added into the raw materials of the low-carbon magnesia carbon brick matrix, so that the mechanical properties of the low-carbon magnesia carbon brick are effectively enhanced. Tests show that compared with the existing low-carbon magnesia carbon brick, the low-carbon magnesia carbon brick prepared by the invention has the advantages that the cold-state rupture strength is improved by 20% after being burnt for 2 hours at 1200 ℃ and is improved by 10% after being burnt for 0.5 hour at 1400 ℃; the low-carbon magnesia carbon brick is applied to refining ladles with the tonnage of more than 180t, the average service life can be prolonged by more than 10 percent, and the low-carbon magnesia carbon brick has important popularization value.
Description
Technical Field
The invention relates to the field of refractory materials, in particular to a method for improving the performance of a low-carbon magnesia carbon brick.
Background
With the development of external refining and continuous casting technologies, a steel ladle is gradually changed into external molten steel refining equipment with complex functions from a pure molten steel container. The extension of the residence time of the molten steel in the ladle and the increase of the tapping temperature make the working environment of the ladle more severe.
Carbon composite refractory materials (such as alumina-magnesia-carbon bricks, magnesia-carbon bricks and the like) have excellent thermal conductivity, better thermal shock resistance, slag resistance and high-temperature performance, and are widely applied to metallurgical furnaces in various links of the steel industry, for example, domestic ladles generally adopt magnesia-alumina-carbon bricks with carbon content of more than 10 wt%. However, when the refractory material is used, the refractory material not only can cause high thermal conductivity of a steel ladle lining and rapid temperature drop of molten steel, but also can cause recarburization of the molten steel, is not suitable for production of low-carbon and ultra-low-carbon high-end steel such as smelting silicon steel, bridge steel, automobile plate steel and the like, and can cause poor oxidation resistance of the refractory material, and the service performance and the service life of the refractory material are reduced. Therefore, the low-carbon formation of the magnesia carbon bricks is an important development direction of the ladle slag line refractory material.
At present, the low-carbon magnesia carbon brick receives high attention from various fields due to the superiorities of reducing self heat conductivity coefficient and total carbon content, carbureting molten steel and the like. However, simply reducing the carbon content in the magnesia carbon brick will cause the deterioration of slag resistance, thermal shock resistance and erosion resistance of the material, shorten the service life, and cannot completely meet the requirements of ladle refining production. In addition, although the phenolic resin binder of the existing low-carbon magnesia carbon brick has a carbon residue rate of over 40 percent, the pyrolytic carbon has low oxidation resistance and high brittleness, and the application value of the pyrolytic carbon in the low-carbon magnesia carbon brick is limited.
Disclosure of Invention
In view of the above, the invention provides a method for improving the performance of a low-carbon magnesia carbon brick.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method for improving the performance of the low-carbon magnesia carbon brick comprises the steps of adding composite fine powder into a low-carbon magnesia carbon brick matrix raw material with the carbon content of 2-6 wt%; the bonding agent in the low-carbon magnesia carbon brick matrix raw material is liquid resin, and 8-15 wt% of boron/copper oxide is added into the liquid resin;
the dosage of the composite fine powder is 1 to 3 weight percent of the sum of the low-carbon magnesia carbon brick matrix raw material and the composite fine powder; the preparation method of the composite fine powder comprises the following steps:
dissolving copper citrate and copper-manganese alloy in distilled water, adding metal silicon powder, stirring, and drying at 110 ℃ for 2-5h to obtain composite silicon powder;
and secondly, uniformly mixing the composite silicon powder and the phenolic resin powder according to the weight ratio of 1.
Preferably, the sum of the weight of the copper citrate and the copper-manganese alloy in the first step is 1wt% of the weight of the metal silicon powder.
Preferably, si in the metal silicon powder is more than or equal to 99 percent, and the granularity is 100-200 meshes; the residual carbon of the phenolic resin powder is more than or equal to 46wt%, and the particle size is less than 75 mu m; the purity of the copper citrate is more than or equal to 99%.
Preferably, the copper manganese alloy contains 28.0-31.0% Mn, 0.9% Fe, 0.1% Sb, 0.1% P, the balance Cu.
Preferably, the liquid resin is liquid phenolic resin, the residual carbon content is more than or equal to 45wt%, and the solid content is more than or equal to 75wt%.
Preferably, the addition amount of boron/copper oxide in the liquid resin is 10wt%, and the boron/copper oxide contains more than or equal to 8% of boron.
Compared with transition metal-containing Fe-Co-Ni catalyst, the Cu-containing composite catalyst based on the chemical vapor deposition principle of the invention can form SiC/SiO in situ 2 The micro-nano fiber network enhances the performance of the low-carbon magnesia carbon brick.
Compared with the traditional low-carbon magnesia carbon brick, the low-carbon magnesia carbon brick has weak comprehensive performances such as strength in a medium temperature range (1100 to 1200 ℃) when being baked on site. When the low-carbon magnesia carbon brick prepared by the method is used in a steel ladle, siC/SiO can be formed by using the baking temperature (1100-1200 ℃) of the steel ladle 2 The composite network of the nanowires and the micro-nanofibers effectively improves the performance of the low-carbon magnesia carbon brick. Specifically, the method comprises the following steps:
the boron/copper oxide of the invention is used as a catalyst to accelerate SiC/SiO 2 And (4) forming a micro-nano fiber network. The copper phase and the copper-manganese alloy derived from the copper citrate can dissolve silicon to generate Cu/Si alloy, thereby reducing the formation temperature of gas-phase silicon oxide and increasing the content of the gas-phase silicon oxide at the medium temperature (1100-1200 ℃). Under the action of copper citrate and copper-manganese alloy, the bonding phase of the phenolic resin is converted into C/SiC combined carbon-ceramic bonding phase from single carbon bond, and SiC/SiO is gradually formed at the same time 2 A composite network of nanowires (the diameter of the nanowires is about 80-150 nm) and micro-nanofibers. On one hand, the pores in the low-carbon magnesia carbon brick are blocked, the oxygen partial pressure is reduced, the formation of the carbon bonding phase and the ceramic bonding phase hinders the oxygen exchange between the material and the surrounding gas, and the graphite is protected from being oxidized seriously; on the other hand, siC/SiO 2 The formation of the composite network ceramic bonding phase of the nano wire and the micro-nano fiber effectively improves the mechanical property of the material.
According to the invention, the composite fine powder and boron/copper oxide are added into the raw materials of the low-carbon magnesia carbon brick matrix, so that the mechanical properties of the low-carbon magnesia carbon brick are effectively enhanced. Tests show that compared with the existing low-carbon magnesia carbon brick, the low-carbon magnesia carbon brick prepared by the invention has the advantages that the cold-state rupture strength is improved by 20% after being burnt for 2 hours at 1200 ℃ and is improved by 10% after being burnt for 0.5 hour at 1400 ℃; the low-carbon magnesia carbon brick is applied to refining ladles with the tonnage of more than 180t, the average service life can be prolonged by more than 10 percent, and the low-carbon magnesia carbon brick has important popularization value.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be noted that each raw material in the following examples is a commercially available product.
The invention provides a method for improving the performance of a low-carbon magnesia carbon brick, which comprises the steps of adding composite fine powder into a low-carbon magnesia carbon brick matrix raw material with the carbon content of 2-6 wt%; wherein, the bonding agent in the raw material of the low-carbon magnesia carbon brick matrix is liquid resin, and 8-15 wt% of boron/copper oxide is added into the liquid resin;
the dosage of the composite fine powder is 1wt% -3wt% of the low-carbon magnesia carbon brick matrix raw material, and the preparation method comprises the following steps:
dissolving copper citrate and copper-manganese alloy in distilled water, adding metal silicon powder, stirring, and drying at 110 ℃ for 2-5h to obtain composite silicon powder; the composite silicon powder comprises copper citrate, copper-manganese alloy and metal silicon powder in parts by weight: (copper citrate + copper manganese alloy): metallic silicon powder = 1;
and secondly, uniformly mixing the composite silicon powder and the phenolic resin powder according to the weight ratio of 1.
The copper phase and the copper-manganese alloy derived from the copper citrate in the composite fine powder can dissolve silicon to generate Cu/Si alloy, so that the formation temperature of the gas-phase silicon oxide is reduced, and the content of the gas-phase silicon oxide at the medium temperature (1100-1200 ℃) is increased. Under the action of copper citrate and copper-manganese alloy, the bonding phase of the phenolic resin is converted into a C/SiC combined carbon-ceramic bonding phase from a single carbon bond, and SiC/SiO is gradually formed at the same time 2 The composite network of the nano wires (the diameter of the nano wires is about 80-150 nm) and the micro-nano fibers can block the pores in the low-carbon magnesia carbon brick, reduce the oxygen partial pressure, prevent the oxygen exchange between the material and the surrounding gas due to the formation of the carbon bonding phase and the ceramic bonding phase and protect the graphite from being oxidized seriously; on the other hand, siC/SiO 2 The formation of the composite network ceramic bonding phase of the nano wire and the micro-nano fiber effectively improves the mechanical property of the material.
Preferably, si in the metal silicon powder is more than or equal to 99 percent, and the granularity is 100-200 meshes; the residual carbon of the phenolic resin powder is more than or equal to 46wt%, and the particle size is less than 75 mu m; the purity of the copper citrate is more than or equal to 99%. The copper manganese alloy contains 28.0-31.0% Mn, 0.9% Fe, 0.1% Sb, 0.1% P, the balance Cu.
Preferably, the liquid resin is a liquid phenolic resin, the residual carbon content of which is more than or equal to 45wt% and the solid content of which is more than or equal to 75wt%. More preferably, the amount of boron/copper oxide added to the liquid resin is 10wt%, and the boron/copper oxide content is 8% or more.
Compared with transition metal-containing Fe-Co-Ni catalyst, the Cu-containing composite catalyst based on the chemical vapor deposition principle of the invention can form SiC/SiO in situ 2 The micro-nano fiber network enhances the performance of the low-carbon magnesia carbon brick.
Compared with the traditional low-carbon magnesia carbon brick, the low-carbon magnesia carbon brick has weak comprehensive performances such as strength in a medium temperature range (1100 to 1200 ℃) when being baked on site. When the low-carbon magnesia carbon brick prepared by the method is used in a steel ladle, siC/SiO can be formed by using the baking temperature (1100-1200 ℃) of the steel ladle 2 The composite network of the nanowires and the micro-nanofibers effectively improves the performance of the low-carbon magnesia carbon brick. Tests show that compared with the existing low-carbon magnesia carbon brick, the low-carbon magnesia carbon brick prepared by the invention has the advantages that the cold-state rupture strength is improved by 20% after being burnt for 2 hours at 1200 ℃ and is improved by 10% after being burnt for 0.5 hour at 1400 ℃; the low-carbon magnesia carbon brick is applied to refining ladles with the tonnage of more than 180t, the average service life can be prolonged by more than 10 percent, and the low-carbon magnesia carbon brick has important popularization value.
Example 1
In the embodiment, 2wt% of composite fine powder and boron/copper oxide are added into a low-carbon magnesia carbon brick base material with a carbon content of 2wt% to improve the performance of the low-carbon magnesia carbon brick, and the sum of the base material and the composite fine powder of the low-carbon magnesia carbon brick is 100wt%. The method specifically comprises the following steps:
the formula of the matrix raw material of the low-carbon magnesia carbon brick with the carbon content of 2wt% is as follows: 97 electric smelting magnesite: 5-3mm 28wt%, 3-1mm 28wt%, 1-0mm 18wt% and 200 mesh 17wt%; 1wt% of metallic aluminum; 1wt% of metallic silicon; 1.5wt% of graphite; 0.5wt% of carbon black; 3wt% of liquid resin (boron/copper oxide-containing);
the residual carbon in the liquid resin (preferably liquid phenolic resin, model: shengquan PF 5323) is more than or equal to 45wt%, and the solid content is more than or equal to 75wt%; 10wt% of boron/copper oxide (boron is more than or equal to 8%) is added into the liquid resin;
when the brick is made, 2wt% of composite fine powder (the sum of the composite fine powder and the matrix raw material of the low-carbon magnesia carbon brick is 100%) is added into the matrix raw material of the low-carbon magnesia carbon brick with the carbon content of 2wt%, and the preparation method of the composite fine powder comprises the following steps:
first, dissolving copper citrate (the purity of the copper citrate is more than or equal to 99%) with distilled water, adding copper-manganese alloy (the copper-manganese alloy contains 28.0-31.0% of Mn, 0.9% of Fe, 0.1% of Sb, 0.1% of P, the balance being Cu) and metallic silicon powder (Si in the metallic silicon powder is more than or equal to 99%, the particle size is 100-200 meshes), stirring, and drying at 110 ℃ for 3h to obtain composite silicon powder; wherein, the weight ratio of copper citrate to copper-manganese alloy to metal silicon powder is 0.7;
and secondly, uniformly mixing the composite silicon powder and phenolic resin powder (the residual carbon content of the phenolic resin powder is more than or equal to 46wt%, the particle size is less than 75 mu m, and the type is Shengquan PF 4112) according to the weight ratio of 1.
The preparation method of the low-carbon magnesia carbon brick comprises the following steps: adding 2wt% of the composite fine powder into a low-carbon magnesia carbon brick matrix raw material with the carbon content of 2wt%, forming by machine pressing, and baking for 8 hours at 200 ℃ to obtain the low-carbon magnesia carbon brick.
The volume density of the low-carbon magnesia carbon brick prepared by the embodiment is 3.22g/cm through testing 3 The apparent porosity is 4.3 percent, the cold bending strength is 7.1MPa at 1200 ℃ for 2h after burning, and the hot bending strength is 15MPa at 1400 ℃ for 0.5 h; the low-carbon magnesia carbon brick of the embodiment is applied to a working lining brick of a 180t refining ladle, and the average service life can reach 50 times.
Example 2
In this example, 1.5wt% of the composite fine powder and boron/copper oxide are added to the matrix material of the low carbon magnesia carbon brick having a carbon content of 3.5wt%, so as to improve the performance of the low carbon magnesia carbon brick, and the total amount of the matrix material and the composite fine powder of the low carbon magnesia carbon brick is 100wt%. The method specifically comprises the following steps:
the formula of the matrix raw material of the low-carbon magnesia carbon brick (the carbon content is 3.5 wt%) is as follows: 97 electric smelting magnesite: 5-3mm 28wt%, 3-1mm 28wt%, 1-0mm 18wt%, and 200 mesh 15.5wt%; 1.5wt% of metallic aluminum; 1wt% of metallic silicon; 2.5wt% of graphite; 1wt% of carbon black; 3wt% of liquid resin (boron/copper oxide-containing);
the liquid resin in the matrix raw material of the low-carbon magnesia carbon brick in the embodiment is the same as that in the embodiment 1;
when the brick is made, 1.5wt% of composite fine powder is added into the matrix raw material of the low-carbon magnesia carbon brick (the sum of the composite fine powder and the matrix raw material of the low-carbon magnesia carbon brick is 100%).
The only difference between the composite fine powder of this example and the composite fine powder of example 1 is the weight ratio of copper citrate, copper-manganese alloy and silicon metal powder. Specifically, in this embodiment, the weight ratio of the copper citrate to the copper-manganese alloy to the metal silicon powder is 0.5.
The preparation method of the low-carbon magnesia carbon brick comprises the following steps: the composite fine powder of the embodiment is added into the matrix raw material of the low-carbon magnesia carbon brick of the embodiment, and is molded by mechanical pressing and baked for 8 hours at 200 ℃ to prepare the low-carbon magnesia carbon brick.
The volume density of the finished low-carbon magnesia carbon brick of the embodiment is 3.16g/cm 3 The apparent porosity is 4.2 percent, the cold bending strength is 7.3MPa after being burnt at 1200 ℃ for 2h, and the hot bending strength is 15MPa at 1400 ℃ for 0.5 h; the finished product of the low-carbon magnesia carbon brick is applied to a working lining brick of a 180t refining ladle, and the average service life can reach 50 times.
Example 3
In the embodiment, 1wt% of composite fine powder and boron/copper oxide are added into a low-carbon magnesia carbon brick matrix raw material with the carbon content of 6wt% to improve the performance of the low-carbon magnesia carbon brick, and the sum of the matrix raw material and the composite fine powder of the low-carbon magnesia carbon brick is 100wt%. The method specifically comprises the following steps:
the formula of the low-carbon magnesia carbon brick base material with the carbon content of 6wt% in the embodiment is as follows: 97 electric smelting magnesite: 28wt% of 5-3mm, 26wt% of 3-1mm, 17wt% of 1-0mm and 16wt% of 200 meshes; 2wt% of metallic aluminum; 1wt% of metallic silicon; 5wt% of graphite; 1wt% of carbon black; 3wt% of liquid resin (boron/copper oxide-containing);
the liquid resin in this example was the same as in example 1;
when the brick is made, 1wt% of composite fine powder (the sum of the composite fine powder and the low-carbon magnesia carbon brick matrix raw material is 100%) is added into the low-carbon magnesia carbon matrix raw material with the carbon content of 6 wt%.
The only difference between the composite fine powder in this example and the composite fine powder in example 1 is the weight ratio of copper citrate, copper-manganese alloy and silicon metal powder. In the embodiment, the weight ratio of the copper citrate to the copper-manganese alloy to the metal silicon powder is 0.4.
The preparation method of the low-carbon magnesia carbon brick comprises the following steps: the composite fine powder of the embodiment is added into the matrix raw material of the low-carbon magnesia carbon brick of the embodiment, and is molded by mechanical pressing and baked for 8 hours at 200 ℃ to prepare the low-carbon magnesia carbon brick.
The volume density of the low-carbon magnesia carbon brick of the embodiment is 3.13g/cm through testing 3 The apparent porosity is 3.5 percent, the cold fracture strength is 8.3MPa at 1200 ℃ for 2h after burning, and the hot fracture strength is 20MPa at 1400 ℃ for 0.5 h. The low-carbon magnesia carbon brick of the embodiment is applied to a working lining brick of a 200t refining ladle, and the average service life can reach 52 times.
Comparative example 1
The present invention uses a low carbon magnesia carbon brick (carbon content 2 wt%) without adding boron/copper oxide and composite fine powder as comparative example 1. Comparative example 1 the formulation of the matrix raw material for the low carbon magnesia carbon brick was the same as in example 1, and no boron/copper oxide was added to the liquid resin in the formulation of the matrix raw material.
The preparation method of the low-carbon magnesia carbon brick comprises the following steps: mixing the raw materials, extruding, and baking at 200 deg.C for 8 hr.
The volume density of the finished low-carbon magnesia carbon brick of the comparative example is 3.06 g/cm 3 The apparent porosity is 4.8 percent, the cold bending strength is 4.9MPa at 1200 ℃ for 2h after burning, and the hot bending strength is 13 MPa at 1400 ℃ for 0.5 h. The brick is applied to a working lining brick of a 180t refining ladle, and the average service life is 45 times.
The properties of the low carbon magnesia carbon bricks obtained in examples 1 to 3 and comparative example 1 are summarized in Table 1.
TABLE 1
As can be seen from Table 1, the low carbon magnesia carbon bricks of examples 1-3 have significantly greater bulk densities than those of comparative example 1; the apparent porosity of examples 1-3 is also significantly higher than that of comparative example 1; the thermal rupture strength at 1400 ℃ for 0.5h of the low-carbon magnesia carbon bricks added with the composite fine powder is far higher than that of the comparative example 1 in the examples 1-3, and the thermal rupture strength at 1400 ℃ for 0.5h of the low-carbon magnesia carbon bricks added with the composite fine powder is improved by more than 10%; compared with the comparative example 1, the low-carbon magnesia carbon brick added with the composite fine powder has the cold fracture strength improved by more than 20 percent at 1200 ℃ for 0.5 h.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (4)
1. A method for improving the performance of a low-carbon magnesia carbon brick is characterized by comprising the following steps: adding composite fine powder into a low-carbon magnesia carbon brick matrix raw material with the carbon content of 2-6 wt%; the bonding agent in the low-carbon magnesia carbon brick matrix raw material is liquid resin, and 8-15 wt% of boron/copper oxide is added into the liquid resin;
the dosage of the composite fine powder is 1 to 3 weight percent of the sum of the low-carbon magnesia carbon brick matrix raw material and the composite fine powder; the preparation method of the composite fine powder comprises the following steps:
dissolving copper citrate and copper-manganese alloy in distilled water, adding metal silicon powder, stirring, and drying at 110 ℃ for 2-5h to obtain composite silicon powder;
si in the metal silicon powder is more than or equal to 99 percent, and the granularity is 100-200 meshes; the purity of the copper citrate is more than or equal to 99 percent; said copper manganese alloy containing 28.0-31.0% Mn, 0.9% Fe, 0.1% Sb, 0.1% P, the balance Cu;
the composite silicon powder comprises copper citrate, copper-manganese alloy and metal silicon powder in parts by weight: (copper citrate + copper manganese alloy): metallic silicon powder = 1;
step two, uniformly mixing the composite silicon powder and the phenolic resin powder according to the weight ratio of 1; wherein the residual carbon of the phenolic resin powder is more than or equal to 46wt%, and the particle size is less than 75 mu m.
2. The method for improving the performance of the low-carbon magnesia carbon brick according to claim 1, wherein: in the first step, the sum of the weight of the copper citrate and the copper-manganese alloy is 1wt% of the weight of the metal silicon powder.
3. The method for improving the performance of the low-carbon magnesia carbon brick according to claim 1, wherein: the liquid resin is liquid phenolic resin, the residual carbon content is more than or equal to 45wt%, and the solid content is more than or equal to 75wt%.
4. The method for improving the performance of the low-carbon magnesia carbon brick according to claim 1 or 3, wherein: the addition amount of boron/copper oxide in the liquid resin is 10wt%, and the boron/copper oxide content is more than or equal to 8%.
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| CN101244940B (en) * | 2008-03-20 | 2013-11-06 | 郑州大学 | Metallic composite low carbon magnesium carbon brick for ladle slag wire and manufacture method thereof |
| CN101423412B (en) * | 2008-11-27 | 2012-07-11 | 中钢集团洛阳耐火材料研究院有限公司 | Method for preparing high performance silicon oxide combining silicon carbide refractory by low-temperature sintering |
| CN106187225B (en) * | 2016-06-30 | 2018-10-30 | 长兴长恒耐火材料股份有限公司 | A kind of anti-erosion magnesia carbon brick and preparation method thereof |
| CN107954697A (en) * | 2017-11-22 | 2018-04-24 | 海城利尔麦格西塔材料有限公司 | A kind of magnesia carbon brick for adding boron carbide and preparation method thereof |
| CN110143807A (en) * | 2019-05-28 | 2019-08-20 | 海城利尔麦格西塔材料有限公司 | A kind of ladle slag line metallic composite low carbon magnesium carbon brick and preparation method thereof |
| CN112028613B (en) * | 2020-09-02 | 2022-07-19 | 江苏苏嘉集团新材料有限公司 | Magnesia carbon brick using catalyst-added phenolic resin |
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| JPH05330904A (en) * | 1992-06-03 | 1993-12-14 | Kyushu Refract Co Ltd | Highly spalling-resistant magnesia carbon brick |
| JP2012031026A (en) * | 2010-08-02 | 2012-02-16 | Shinagawa Refractories Co Ltd | Alumina-magnesia-based refractory brick and method for producing the same |
| CN108129136A (en) * | 2018-01-04 | 2018-06-08 | 武汉科技大学 | Copper converter lower part magnesia-forsterite-carbon composite and preparation method thereof |
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