CN112939577B - Unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles and preparation method - Google Patents
Unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles and preparation method Download PDFInfo
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Abstract
The invention relates to the technical field of refractory materials, in particular to an unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles. The unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles is prepared from the following raw materials in parts by weight: 20-60 parts of magnesia-calcium sand, 25-75 parts of magnesia, 0.1-2.5 parts of zirconia, 3-10 parts of graphite, 3-15 parts of co-ground powder and 2-4 parts of bonding agent. According to the invention, the medium/high temperature expansion performance of the unburned magnesium-calcium-carbon brick particles and the matrix is adjusted, so that the re-burning line change of the product at medium/high temperature is a positive value, and the phenomenon that the steel is sandwiched in a permanent layer due to the fact that a masonry body has gaps caused by large temperature fluctuation of a magnesium-calcium-carbon working layer in the turnover process of a steel ladle is avoided.
Description
Technical Field
The invention relates to the technical field of refractory materials, in particular to an unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles.
Background
The magnesia-calcium-carbon brick has good high-temperature vacuum stability, thermal shock resistance, high alkalinity/acid slag corrosion and permeation resistance and molten steel purification performance, and has good use effect on the external refining furnace. However, the steel ladle for building the magnesia-calcium-carbon bricks often has the situation of steel clamping in a permanent layer in the using process, so that the refractory materials are dismantled in advance, and the resource waste situation is caused.
The permanent layer steel of the magnesium-calcium carbon steel ladle is mainly formed by two reasons: (1) under the condition that the ladle hot ladle is stopped for a long time or the cold ladle is not baked sufficiently, as the change of the reburning line of the magnesia-calcium-carbon brick is generally a negative value, brick joints can appear in the magnesia-calcium-carbon brick masonry, and molten steel/slag can permeate to a permanent layer along the brick joints to cause steel clamping. (2) When the slide plate nozzle is replaced and the air brick is blown and burned on the hot repair platform, the magnesia-calcium-carbon brick in the 12 o 'clock direction is displaced under the action of self weight, and the change of the re-burning line of the magnesia-calcium-carbon brick is generally a negative value, so that the gap between the magnesia-calcium-carbon ladle in the 12 o' clock direction and the permanent layer is larger and larger, and the permanent layer is easy to cause steel clamping.
Therefore, how to prepare the unburned magnesia-calcium-carbon brick for preventing the steel ladle from being sandwiched by the permanent layers to solve the problem of 'permanent layer sandwiched steel' in the prior art is a technical problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In order to make up the defects of the magnesia-calcium-carbon brick for smelting clean steel, the invention researches a non-fired magnesia-calcium-carbon brick for ladle external refining, which has the excellent characteristics of corrosion resistance, good thermal shock stability and the like of the magnesia-calcium-carbon brick, has unique re-firing micro-expansion performance, can ensure the safe and continuous turnover of a ladle, and can avoid the condition that steel is sandwiched between permanent layers of the ladle.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of a steel ladle, which comprises the following raw materials in parts by weight:
41-55 parts of calcium magnesite with the granularity of 0.05-5mm, 36-50 parts of fused magnesite with the granularity of 0.05-5mm, 3-10 parts of graphite with the granularity of 80-100 meshes, 0.1-2.5 parts of zirconia with the granularity of 0.2-3mm, 3-15 parts of co-ground powder and 2-4 parts of bonding agent.
Preferably, the density of the magnesia-calcium sand is more than or equal to 3.25g/cm 3 (ii) a In the magnesia-calcium sand, the mass percent of CaO is 18-58%, the mass percent of MgO is 40-80%, and Fe 2 O 3 The mass percentage content is less than or equal to 0.1 percent, and the ignition loss is less than or equal to 0.3 percent.
Preferably, the magnesia-calcium sand particles comprise 16-20 parts of magnesia-calcium sand with the particle size of 3-5mm, 22-28 parts of magnesia-calcium sand with the particle size of 1-3mm and 3-7 parts of magnesia-calcium sand with the particle size of 0.05-1 mm.
Preferably, the density of the fused magnesia is more than or equal to 3.45g/cm 3 The mass of MgO in the fused magnesia is hundredThe content is more than or equal to 96 percent, and the ignition loss is less than or equal to 0.3 percent.
Preferably, the fused magnesite grain comprises 6-10 parts of fused magnesite with the grain diameter of 3-5mm, 3-7 parts of fused magnesite with the grain diameter of 1-3mm and 27-33 parts of fused magnesite with the grain diameter of 0.05-1 mm.
Preferably, ZrO in the zirconia 2 The mass percentage content of the compound is more than or equal to 95 percent; the solid content of the graphite with the granularity of 80-100 meshes is more than or equal to 94.0 wt%, and the mass percentage of the water content is less than or equal to 0.05%.
Preferably, the co-milled powder consists of the following raw materials: fused magnesia with the granularity of less than 0.05mm, metal magnesium powder, lanthanum oxide micro powder, titanium oxide micro powder, alpha-alumina micro powder, asphalt, urotropine and carbon nano tubes, wherein the raw materials comprise the following components in percentage by weight: 2-8: 0.1-1.5: 0.1-1.5: 0.1-1.5: 0.1-1.5: 0.1-2: 0.1-2: 0.01-1.
Preferably, the density of the fused magnesia is more than or equal to 3.45g/cm 3 The MgO content in the fused magnesia is more than or equal to 96 percent by mass, and the ignition loss is less than or equal to 0.3 percent; the metal magnesium powder is 320-mesh and 330-mesh, and the mass percentage of magnesium is more than or equal to 99.0 percent; the granularity of the lanthanum oxide micro powder is 5-100 mu m, and the mass percentage content of lanthanum oxide is more than or equal to 99.0 percent; the granularity of the titanium oxide micro powder is 10-100nm, and the mass percentage content of the titanium oxide is more than or equal to 99.0%; the particle size of the alpha-alumina micro powder is 1-2 mu m, Al 2 O 3 The mass percentage content of the compound is more than or equal to 99.0 percent; the asphalt is 150-200 meshes, and the mass percentage content of the solid content is more than or equal to 76%; the length of the carbon nano tube is 25-100 mu m, and the diameter is 0.2-2.5 nm.
Preferably, the bonding agent is anhydrous phenolic resin with the viscosity of 8000-11000 Pa.S, wherein the solid content is more than or equal to 80 wt%, the residual carbon is more than or equal to 20 wt%, and the water content is less than or equal to 0.2 wt%.
The invention also aims to provide a preparation method of the unburned magnesia-calcium-carbon brick for preventing steel from being sandwiched in the permanent layer of the steel ladle, which comprises the following steps:
(1) preparing the co-ground powder according to a proportion, and co-grinding the co-ground powder in a vibration mill for 10-15 min;
(2) dry-mixing the magnesia-calcium sand particles, the fused magnesia particles and the zirconia particles according to the proportion for 2-3min, then slowly adding the binding agent at one time within 2min, adding the graphite after wet mixing for 3-5min, adding the co-ground powder obtained in the step (1) after mixing for 5-8min, and discharging after mixing for 20-30 min;
(3) forming by a brick press to obtain green bricks;
(4) the green brick is heat treated in a tunnel kiln, the temperature of the kiln is required to be 260-350 ℃ before entering the kiln, a fan is started, the temperature is kept at 260-350 ℃ for 10-14h, and then the green brick is taken out of the kiln and sorted to obtain a finished product.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. compared with the prior art, the addition of 0.2-3mm zirconia particles can generate t-ZrO at 800-1000 DEG C 2 To m-ZrO 2 The shift-type phase transition, accompanied by a volume expansion of about 4.7%, can offset the volume shrinkage of conventional magnesia-calcium-carbon unburned bricks in medium/high temperature environments.
2. Compared with the prior art, by adding 320-mesh 330-mesh metal magnesium powder, 1-2 μm alpha-alumina micro powder, 5-100 μm lanthanum oxide micro powder and 10-100nm titanium oxide micro powder, the thermal shock stability, high-temperature strength, oxidation resistance and hydration resistance of the material can be improved, and the medium/high-temperature volume expansion performance of the matrix material can be regulated by regulating and controlling the generation rate and quantity of in-situ spinel, the growth rate of periclase and periclase phase grains and the content and distribution of a glass phase.
3. Compared with the prior art, the medium/high temperature expansion performance of the unburned magnesium calcium carbon brick particles and the matrix material is adjusted and matched, so that the product has the micro-expansion characteristic in the use process, cracking does not occur, and permanent steel interlayer caused by volume shrinkage of the unburned magnesium calcium carbon brick in the use process is avoided.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, all starting materials are known commercially available products, and relevant parameters for some of the starting materials are provided for reference:
the density of the magnesia-calcium sand is more than or equal to 3.25g/cm 3 The mass percent of CaO in the magnesia-calcium sand is 18-58%, the mass percent of MgO is 40-80%, and Fe 2 O 3 The mass percentage content is less than or equal to 0.1 percent, and the ignition loss is less than or equal to 0.3 percent; the density of the fused magnesia is more than or equal to 3.45g/cm 3 The MgO content in the fused magnesia is more than or equal to 96 percent by mass, and the ignition loss is less than or equal to 0.3 percent; ZrO in zirconia 2 The mass percentage content of the compound is more than or equal to 95 percent; the granularity of the graphite is 80-100 meshes, the solid content is more than or equal to 94.0 wt%, and the mass percentage of the water content is less than or equal to 0.05%; the metal magnesium powder is 320-mesh and 330-mesh, and the mass percentage of magnesium is more than or equal to 99.0 percent; the granularity of the lanthanum oxide micro powder is 5-100 mu m, and the mass percentage content of lanthanum oxide is more than or equal to 99.0 percent; the granularity of the titanium oxide micro powder is 10-100nm, and the mass percentage content of the titanium oxide is more than or equal to 99.0 percent; the grain size of the alpha-alumina micro powder is 1-2 mu m, Al 2 O 3 The mass percentage content of the compound is more than or equal to 99.0 percent; the asphalt is 150-200 meshes, and the mass percentage content of the solid content is more than or equal to 76 percent; the length of the carbon nano tube is 25-100 mu m, and the diameter is 0.2-2.5 nm; the bonding agent is anhydrous phenolic resin with the viscosity of 8000-11000 Pa.S, wherein the solid content is more than or equal to 80 wt%, the residual carbon is more than or equal to 20 wt%, and the water content is less than or equal to 0.2 wt%.
Example 1
(1) Preparing co-milled powder: the raw materials comprise: fused magnesite with the granularity of less than 0.05mm, 320-mesh metal magnesium powder, lanthanum oxide micro powder with the granularity of 5 mu m, titanium oxide micro powder with the granularity of 10nm, alpha-alumina micro powder with the granularity of 1 mu m, 150-mesh asphalt, urotropine, carbon nano tubes with the length of 25 mu m and the diameter of 0.2nm, wherein the adding proportion of the raw materials is as follows: 2: 0.1: 0.1: 0.1: 0.1: 0.1: 0.1: 0.01, putting the raw materials into a vibration mill, and milling for 10 min;
(2) taking 16 parts of calcium magnesite with the grain diameter of 3-5mm, 22 parts of calcium magnesite with the grain diameter of 1-3mm and 3 parts of calcium magnesite with the grain diameter of 0.05-1 mm; 6 parts of fused magnesite with the grain diameter of 3-5mm, 3 parts of fused magnesite with the grain diameter of 1-3mm and 27 parts of fused magnesite with the grain diameter of 0.05-1 mm; 0.1 part of zirconia with the granularity of 0.2 mm; dry mixing for 2min, slowly adding 2 parts of anhydrous phenolic resin with the viscosity of 8000Pa & S at one time within 2min, wet mixing for 3min, adding 3 parts of graphite with the particle size of 80 meshes, mixing for 5min, adding 3 parts of the co-ground powder obtained in the step (1), mixing for 20min, and discharging.
(3) Forming by a brick press to obtain green bricks;
(4) and (3) carrying out heat treatment on the green bricks by using a tunnel kiln, wherein the kiln temperature is required to be 260 ℃ before entering the kiln, a fan is started, the temperature is kept at 260 ℃ for 10 hours, and then the green bricks are taken out of the kiln and sorted to obtain a finished product.
Example 2
(1) Preparing co-milled powder: the raw materials comprise: fused magnesite with the granularity of less than 0.05mm, 325-mesh metal magnesium powder, lanthanum oxide micro powder with the granularity of 55 mu m, titanium oxide micro powder with the granularity of 60nm, alpha-alumina micro powder with the granularity of 1.5 mu m, pitch with 170 meshes, urotropine, carbon nano tubes with the length of 65 mu m and the diameter of 1.4nm, and the adding proportion of the raw materials is as follows: 5: 0.9: 1.0: 0.8: 0.7: 1.0: 1.1: 0.5, putting the raw materials into a vibration mill, and grinding for 13 min;
(2) taking 18 parts of calcium magnesia with the grain diameter of 3-5mm, 25 parts of calcium magnesia with the grain diameter of 1-3mm and 5 parts of calcium magnesia with the grain diameter of 0.05-1 mm; 8 parts of fused magnesia with the grain diameter of 3-5mm, 5 parts of fused magnesia with the grain diameter of 1-3mm and 30 parts of fused magnesia with the grain diameter of 0.05-1 mm; 1.3 parts of zirconia with the granularity of 2 mm; dry-mixing for 2.5min, slowly adding 3 parts of anhydrous phenolic resin with viscosity of 10000 Pa.S at one time within 2min, wet-mixing for 4min, adding 6 parts of graphite with particle size of 90 meshes, mixing for 7min, adding 9 parts of the co-ground powder obtained in the step (1), mixing for 25min, and discharging.
(3) Forming by a brick press to obtain green bricks;
(4) and (3) carrying out heat treatment on the green bricks by using a tunnel kiln, wherein the kiln temperature is required to be 300 ℃ before entering the kiln, starting a fan, keeping the temperature at 300 ℃ for 12h, and then taking out the green bricks from the kiln and sorting to obtain a finished product.
Example 3
(1) Preparing co-milled powder: the raw materials comprise: fused magnesite with the granularity of less than 0.05mm, 330-mesh metal magnesium powder, lanthanum oxide micro powder with the granularity of 100 mu m, titanium oxide micro powder with the granularity of 100nm, alpha-alumina micro powder with the granularity of 2 mu m, asphalt with 200 meshes, urotropine, carbon nano tubes with the length of 100 mu m and the diameter of 2.5nm, wherein the adding proportion of the raw materials is as follows: 8: 1.5: 1.5: 1.5: 1.5: 2: 2: 1, putting the mixture into a vibration mill for co-milling for 15 min;
(2) taking 20 parts of calcium magnesite with the grain diameter of 3-5mm, 28 parts of calcium magnesite with the grain diameter of 1-3mm and 7 parts of calcium magnesite with the grain diameter of 0.05-1 mm; 10 parts of fused magnesia with the grain diameter of 3-5mm, 7 parts of fused magnesia with the grain diameter of 1-3mm and 33 parts of fused magnesia with the grain diameter of 0.05-1 mm; 2.5 parts of zirconia with the granularity of 3 mm; dry-mixing for 3min, slowly adding 4 parts of anhydrous phenolic resin with the viscosity of 11000 Pa.S in 2min at one time, wet-mixing for 5min, adding 10 parts of graphite with the particle size of 100 meshes, mixing for 8min, adding 15 parts of the co-ground powder obtained in the step (1), mixing for 30min, and discharging.
(3) Forming by a brick press to obtain green bricks;
(4) and (3) carrying out heat treatment on the green bricks by using a tunnel kiln, wherein the temperature of the kiln is required to be 350 ℃ before entering the kiln, starting a fan, keeping the temperature at 350 ℃ for 14h, and then taking out of the kiln and sorting to obtain a finished product.
Comparative example 1
(1) Preparing co-milled powder: the raw materials comprise: fused magnesite with the granularity of less than 0.05mm, 325-mesh metal magnesium powder, titanium oxide micro powder with the granularity of 60nm, alpha-alumina micro powder with the granularity of 1.5 mu m, pitch with 170 meshes, urotropine, carbon nano tubes with the length of 65 mu m and the diameter of 1.4nm, wherein the adding proportion of the raw materials is as follows: 5: 0.9: 0.8: 0.7: 1.0: 1.1: 0.5, putting the raw materials into a vibration mill, and grinding for 13 min;
(2) taking 18 parts of calcium magnesia with the grain diameter of 3-5mm, 25 parts of calcium magnesia with the grain diameter of 1-3mm and 5 parts of calcium magnesia with the grain diameter of 0.05-1 mm; 8 parts of fused magnesia with the grain diameter of 3-5mm, 5 parts of fused magnesia with the grain diameter of 1-3mm and 30 parts of fused magnesia with the grain diameter of 0.05-1 mm; dry-mixing for 2.5min, slowly adding 3 parts of anhydrous phenolic resin with viscosity of 10000Pa & S at one time within 2min, wet-mixing for 4min, adding 6 parts of graphite with particle size of 90 meshes, mixing for 7min, adding 9 parts of the co-ground powder obtained in the step (1), mixing for 25min, and discharging.
(3) Forming by a brick press to obtain green bricks;
(4) and (3) carrying out heat treatment on the green bricks by using a tunnel kiln, wherein the kiln temperature is required to be 300 ℃ before entering the kiln, starting a fan, keeping the temperature at 300 ℃ for 12h, and then taking out the green bricks from the kiln and sorting to obtain a finished product.
Comparative example 2
(1) Preparing co-milled powder: the raw materials comprise: fused magnesite with the granularity of less than 0.05mm, 325-mesh metal magnesium powder, lanthanum oxide micro powder with the granularity of 55 mu m, alpha-alumina micro powder with the granularity of 1.5 mu m, pitch with 170 meshes, urotropine, carbon nano tubes with the length of 65 mu m and the diameter of 1.4nm, wherein the adding proportion of the raw materials is as follows: 5: 0.9: 1.0: 0.7: 1.0: 1.1: 0.5, putting the raw materials into a vibration mill, and grinding for 13 min;
(2) taking 20 parts of magnesia-calcium sand with the grain diameter of 5-15mm, 12 parts of magnesia-calcium sand with the grain diameter of 3-5mm, 15 parts of magnesia-calcium sand with the grain diameter of 1-3mm and 26 parts of magnesia-calcium sand with the grain diameter of 0.05-1 mm; 8 parts of fused magnesia with the grain diameter of 3-5mm, 5 parts of fused magnesia with the grain diameter of 1-3mm and 30 parts of fused magnesia with the grain diameter of 0.05-1 mm; 1.3 parts of zirconia with the granularity of 2 mm; dry-mixing for 2.5min, slowly adding 3 parts of anhydrous phenolic resin with viscosity of 10000 Pa.S at one time within 2min, wet-mixing for 4min, adding 6 parts of graphite with particle size of 90 meshes, mixing for 7min, adding 9 parts of the co-ground powder obtained in the step (1), mixing for 25min, and discharging.
(3) Forming by a brick press to obtain green bricks;
(4) and (3) carrying out heat treatment on the green bricks by using a tunnel kiln, wherein the kiln temperature is required to be 300 ℃ before entering the kiln, starting a fan, keeping the temperature at 300 ℃ for 12h, and then taking out the green bricks from the kiln and sorting to obtain a finished product.
The change of a re-burning line, the erosion resistance and the thermal shock stability of the unburned magnesia-calcium-carbon bricks prepared in the examples 1 to 3 and the comparative examples 1 to 2 are shown in a table 1, wherein the change of the re-burning line is characterized in that the corresponding samples are subjected to heat preservation for 3 hours under the condition of carbon burying at 1100 ℃ and 1600 ℃ respectively; the erosion resistance characterization method comprises the steps of enabling a corresponding sample to be heated at a temperature rise rate of 4-6 ℃/min below 1000 ℃, at a temperature rise rate of 3-4 ℃/min above 1000 ℃, keeping the temperature at the highest temperature of 1600 ℃ for 3 hours; the thermal shock stability characterization method is to calculate the retention rate of the residual breaking strength of a corresponding sample after thermal shock for 3 times at 1100 ℃ by using an air cooling method.
TABLE 1
As can be seen from the characteristics of the re-burning line change, the erosion resistance and the thermal shock stability of the unburned MgO-C bricks prepared in examples 1-3 and comparative examples 1-2, comparative example 1 and example 1-3 are different in the composition of the co-ground powder, and zirconia particles are not added, so that the re-burning line change, the erosion resistance and the thermal shock stability of the sample are obviously lower than those of examples 1-3. The comparative example 2 is different from the compositions of the cofired powders of examples 1 to 3, and the used magnesia-calcium sand has different particle sizes, so that after the temperature is kept for 3 hours at 1100 ℃ and 1600 ℃ under the condition of carbon burying, the shrinkage defect is still caused, the steel ladle permanent layer clamping condition is still caused, and the erosion resistance and the thermal shock resistance are obviously lower than those of examples 1 to 3.
The above embodiments show that the unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles has unique re-sintering micro-expansion performance, can ensure safe and continuous turnover of steel ladles, can avoid the condition that steel is sandwiched between permanent layers of steel ladles, and has excellent erosion resistance and thermal shock stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles is characterized by comprising the following raw materials in parts by weight:
41-55 parts of calcium magnesite with the granularity of 0.05-5mm, 36-50 parts of fused magnesite with the granularity of 0.05-5mm, 3-10 parts of graphite with the granularity of 80-100 meshes, 0.1-2.5 parts of zirconia with the granularity of 0.2-3mm, 3-15 parts of co-ground powder and 2-4 parts of bonding agent;
the co-milled powder consists of the following raw materials: fused magnesia with the granularity of less than 0.05mm, metal magnesium powder, lanthanum oxide micro powder, titanium oxide micro powder, alpha-alumina micro powder, asphalt, urotropine and carbon nano tubes, wherein the raw materials comprise the following components in percentage by weight: 2-8: 0.1-1.5: 0.1-1.5: 0.1-1.5: 0.1-1.5: 0.1-2: 0.1-2: 0.01-1.
2. According toThe unburned magnesium-calcium-carbon brick for preventing steel from being included in permanent steel ladle layer as recited in claim 1, wherein the density of the magnesium-calcium sand is not less than 3.25g/cm 3 (ii) a In the magnesia-calcium sand, the mass percent of CaO is 18-58%, the mass percent of MgO is 40-80%, and Fe 2 O 3 The mass percentage content is less than or equal to 0.1 percent, and the ignition loss is less than or equal to 0.3 percent.
3. The unburned magnesium calcium carbon brick for preventing steel inclusion in a permanent layer of a steel ladle according to claim 2, wherein the magnesium calcium sand particles comprise 16-20 parts of magnesium calcium sand with a particle size of 3-5mm, 22-28 parts of magnesium calcium sand with a particle size of 1-3mm, and 3-7 parts of magnesium calcium sand with a particle size of 0.05-1 mm.
4. The unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles as claimed in claim 1, wherein the density of fused magnesia is not less than 3.45g/cm 3 The MgO content in the fused magnesia is more than or equal to 96 percent by mass, and the ignition loss is less than or equal to 0.3 percent.
5. The unburned magnesite-calcium-carbon brick for preventing steel from being included in the permanent layer of the steel ladle as claimed in claim 4, wherein the fused magnesite grain includes 6-10 parts of fused magnesite with a grain size of 3-5mm, 3-7 parts of fused magnesite with a grain size of 1-3mm, and 27-33 parts of fused magnesite with a grain size of 0.05-1 mm.
6. The unburned magnesium-calcium-carbon brick for preventing steel from being included in permanent layer of steel ladle as claimed in claim 1, wherein ZrO in zirconia 2 The mass percentage content of the compound is more than or equal to 95 percent; the solid content of the graphite with the granularity of 80-100 meshes is more than or equal to 94.0 wt%, and the mass percentage of the water content is less than or equal to 0.05%.
7. The unburned magnesium-calcium-carbon brick for preventing steel from being sandwiched between permanent layers of steel ladles as claimed in claim 1, wherein the density of fused magnesia is not less than 3.45g/cm 3 The MgO content in the fused magnesia is more than or equal to 96 percent by mass, and the ignition loss is less than or equal to 0.3 percent; the metal magnesium powder is 320-mesh and 330-mesh, and the mass percentage of magnesium is more than or equal to 99.0 percent; the granularity of the lanthanum oxide micro powder is 5-100 mu m,the mass percentage content of lanthanum oxide is more than or equal to 99.0 percent; the granularity of the titanium oxide micro powder is 10-100nm, and the mass percentage content of the titanium oxide is more than or equal to 99.0%; the particle size of the alpha-alumina micro powder is 1-2 mu m, Al 2 O 3 The mass percentage content of the compound is more than or equal to 99.0 percent; the asphalt is 150-200 meshes, and the mass percentage content of the solid content is more than or equal to 76%; the length of the carbon nano tube is 25-100 mu m, and the diameter is 0.2-2.5 nm.
8. The unburned magnesium-calcium-carbon brick for preventing steel from being permanently laminated in a ladle as claimed in claim 1, wherein the binder is anhydrous phenolic resin with viscosity of 8000-11000 Pa-S, wherein the solid content is greater than or equal to 80 wt%, the residual carbon is greater than or equal to 20 wt%, and the water content is less than or equal to 0.2 wt%.
9. The method for preparing unburned magnesium-calcium-carbon bricks for preventing steel from being laminated in permanent steel ladles according to any one of claims 1 to 8, which comprises the following steps:
(1) preparing the co-ground powder according to a proportion, and co-grinding the co-ground powder in a vibration mill for 10-15 min;
(2) dry-mixing the magnesia-calcium sand particles, the fused magnesia particles and the zirconia particles according to the proportion for 2-3min, then slowly adding the binding agent at one time within 2min, adding the graphite after wet mixing for 3-5min, adding the co-ground powder obtained in the step (1) after mixing for 5-8min, and discharging after mixing for 20-30 min;
(3) forming by a brick press to obtain green bricks;
(4) the green brick is heat treated in a tunnel kiln, the temperature of the kiln is required to be 260-350 ℃ before entering the kiln, a fan is started, the temperature is kept at 260-350 ℃ for 10-14h, and the green brick is taken out of the kiln and sorted to obtain a finished product.
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