CN115160000B - Composite pug for producing functional refractory material for steelmaking and preparation method and application thereof - Google Patents
Composite pug for producing functional refractory material for steelmaking and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite pug for producing a functional refractory material for steelmaking and a preparation method and application thereof. The provided composite pug comprises the following components in percentage by mass: 88 to 92 percent of rare earth raw material, 3 to 5 percent of crystalline flake graphite, 0.5 to 1.5 percent of boron carbide and 4 to 6 percent of phenolic resin. The functional refractory material prepared from the composite pug provided by the invention can effectively avoid the reaction of rare earth in molten steel and magnesium, high-alumina, silicate refractory materials and the like, and further can effectively avoid pouring interruption or production accidents.
Description
Technical Field
The invention belongs to the technical field of metallurgical refractory materials, and particularly relates to a composite pug for producing a functional refractory material for steelmaking as well as a preparation method and application thereof.
Background
The smelting of the rare earth steel is beneficial to improving the quality level of steel materials, and reaches or exceeds the product quality level of foreign advanced enterprises. With the continuous and intensive research, researchers find that the addition of rare earth into steel has various beneficial effects, including purification, modification, microalloying, hydrogen capture and the like, and the rare earth can improve the structure, the tensile strength, the wear resistance, the drawability and the fatigue resistance of steel. However, the production of rare earth has a plurality of bottleneck problems, and under the high-temperature state of continuous casting, the Rare Earth (RE) in the molten steel is very active and can react with magnesium, high-alumina and silicate refractory materials as follows:
4RE+3SiO 2 ＝2RE 2 O 3 +3Si
2RE+Al 2 O 3 ＝RE 2 O 3 +2Al
2RE+3MgO＝RE 2 O 3 +3Mg
further leading to the plug rod out of control, the nozzle blockage and in severe cases to the pouring interruption or production accident. The covering agent, the dry material, the crystallizer protecting slag and the like in the middle ladle can generate the reaction, and the quality of the inner part and the outer part of the casting blank is widely influenced.
The technology of applying rare earth oxide to improve refractory materials in the field of refractory materials is still in the exploration stage, at present, rare earth oxide is usually added into basic refractory materials such as magnesium refractory materials, magnesium spinel refractory materials and the like to reduce the apparent porosity of the refractory materials, improve the compactness, high-temperature breaking strength, thermal shock resistance and the like of the refractory materials, but the refractory materials still have the phenomena of water gap blockage and plug rod runaway.
Disclosure of Invention
In order to solve one or more problems in the prior art, the invention provides a composite pug for producing a functional refractory material for steelmaking, which comprises the following components in percentage by mass: 88 to 92 percent of rare earth raw material, 3 to 5 percent of crystalline flake graphite, 0.5 to 1.5 percent of boron carbide and 4 to 6 percent of phenolic resin;
wherein the rare earth raw material is obtained by the following steps:
1) Mixing rare earth powder with the purity of more than or equal to 99.0 percent and aluminum powder with the purity of more than or equal to 99.0 percent according to the molar ratio of the rare earth to the Al of (0.5-3) to 1 to obtain an intermediate;
2) The intermediate obtained in the step 1) is sintered for 3.5 to 4.5 hours at the temperature of 1500 to 1700 ℃.
In some embodiments, the molar ratio of rare earth to Al in step 1) is (1-2): 1.
In some embodiments, the temperature in step 2) is 1550 to 1650 ℃.
In some embodiments, step 2) further comprises crushing, screening and grinding the product obtained by firing to obtain a powder with a particle size of less than 0.5mm, and obtaining the rare earth raw material.
In some embodiments, the particle size of the rare-earth powder in step 1) is < 325 mesh, and the particle size of the aluminum powder is < 325 mesh.
In some embodiments, the rare earth powder comprises rare earth cerium powder, rare earth lanthanum powder, rare earth neodymium powder, rare earth yttrium powder, or mixtures thereof.
In some embodiments, the rare earth powder is a rare earth cerium powder.
The invention also provides the application of the composite pug in the production of functional refractory materials for steelmaking.
In some embodiments, the functional refractory for steelmaking comprises: continuous casting submerged nozzle, continuous casting tundish stopper, retaining wall, brick cup, dam and tundish working layer.
The invention also provides a preparation method of the composite pug, which comprises the step of mixing the components of the composite pug in a granulator for 15-30 minutes.
The composite pug for producing the functional refractory material for steelmaking provided by the invention is formed by mixing rare earth raw materials, crystalline flake graphite, boron carbide and phenolic resin, and an aluminate rare earth carbon layer of the refractory material, which is in direct contact with molten steel, can be formed in the preparation of the functional refractory material for steelmaking, wherein the aluminate rare earth carbon layer has lower apparent porosity (less than or equal to 20%) and higher volume density (more than or equal to 3.0 g/cm) 3 ) And the breaking strength (more than or equal to 5.9 MPa), can effectively avoid the reaction of the rare earth in the molten steel with magnesium, high-alumina, silicate refractory materials and the like, and further can effectively avoid the pouring interruption or production accidents in the production process of the rare earth steel.
Drawings
FIG. 1 is a microscopic crystal structure of a rare earth raw material for producing a refractory for steel making according to the present invention;
FIG. 2 is a schematic structural view of a continuous casting submerged entry nozzle manufactured according to the present invention;
FIG. 3 is a photograph of a real object of a continuous casting immersion nozzle manufactured according to the present invention;
FIG. 4 is a schematic structural view of a continuous casting tundish stopper prepared according to the present invention;
FIG. 5 is a photograph of a physical object of a continuous casting tundish stopper prepared according to the present invention;
fig. 6 is a photograph showing the inner diameter of the continuous casting submerged nozzle of application example 1 after use.
Detailed Description
The present invention will be described in detail below with reference to specific examples, which are intended to facilitate understanding of the present invention and are not intended to limit the present invention.
Example 1: rare earth raw material for producing refractory material for steelmaking, refractory material composite pug for steelmaking and preparation of functional refractory material
(1) Preparation of rare earth raw material for producing refractory material for steelmaking
1.1 Uniformly mixing rare earth cerium powder (granularity is less than 325 meshes) with the purity of more than or equal to 99.0% and aluminum powder (granularity is less than 325 meshes) with the purity of more than or equal to 99.0% according to the molar ratio of Ce to Al of 1;
1.2 Loading the intermediate obtained in the step 1) into a shuttle kiln, heating to 1600 ℃, keeping for 4 hours, firing to obtain a composite oxide of rare earth cerium and aluminum, cooling along with the kiln, crushing, screening and grinding, selecting composite oxide powder with the granularity of less than 0.5mm as a rare earth raw material for producing the refractory material for steelmaking, and naming the composite oxide powder as the rare earth raw material 1, wherein the microstructure is shown as a rare earth raw material 1, and the A, B, C and D amplitudes are respectively represented as microstructure diagrams which are amplified by 1000 times, 2000 times, 4000 times and 6000 times.
(2) Preparation of refractory material composite pug for steelmaking
The method for producing the refractory material composite pug for steelmaking by using the rare earth raw material 1 prepared in the step (1) comprises the following steps of batching and granulating:
2.1 Placing the rare earth raw material 1 prepared in the step (1) (the addition amount is 90% of the total weight of the refractory pug, and in some embodiments, 88% -92%) in a granulator, adding crystalline flake graphite (obtained from Qingdao Ming, and the addition amount is 4% of the total weight of the refractory pug, and in some embodiments, 3% -5%), boron carbide (obtained from peony river boron carbide Co., ltd., the addition amount is 1% of the total weight of the refractory pug, and in some embodiments, 0.5% -1.5%), and phenolic resin (the addition amount is 5% of the total weight of the refractory pug, and in some embodiments, 4% -6%) as a bonding agent, mixing for 15-30 minutes to prepare the refractory composite pug (the particle size can be adjusted according to actual needs, for example, 0.05-1mm and the like), and naming the prepared composite pug as pug 1.
(3) Preparation of functional refractory material for steelmaking
The step is exemplified by the production of a continuous casting submerged nozzle and a continuous casting tundish stopper for steel making, and the functional refractory material can also be a retaining wall, a brick cup, a dam, a tundish working layer and other parts which can be in direct contact with molten steel. Preparing a functional refractory material by using the pug 1 obtained in the step (2) (mainly, a cerium aluminate carbon layer at a part of the functional refractory material, which is directly contacted with molten steel, is formed by the pug 1 obtained in the step (2)), and the method comprises the following steps of: filling a mold → isostatic pressing → curing → sintering → processing → glazing → flaw detection → packaging, which specifically comprises the following operations:
3.1 According to the schematic structural diagram of the continuous casting submerged nozzle shown in fig. 2, the pug 1 obtained in step (2), the bulk aluminum carbon layer pug (pug made of brown corundum and crystalline flake graphite), and the slag line zirconium carbon layer pug (pug made of zirconia and crystalline flake graphite) are filled into a mold, and then are subjected to processes of molding, curing (drying the pug at 100-120 ℃ for 5-7 hours), firing (keeping the cured pug at 1500-1700 ℃ for 2-4 hours), processing, glazing, X-ray flaw detection and the like, so that a qualified finished product is finally obtained, which is named as the continuous casting submerged nozzle 1. As shown in fig. 3, a physical diagram of the continuous casting submerged entry nozzle 1 is shown. According to the schematic structure shown in fig. 2, the continuous casting submerged nozzle is a hollow structure, one end of the inlet section 10 is a horn-shaped and is formed by the main aluminum carbon layer mud, the other end of the inlet section 11 is a cylindrical outlet section and is formed by the mud 1, the main aluminum carbon layer mud and the slag line zirconium carbon layer mud, wherein the outer diameter of the horn-shaped mouth of the inlet section 10 is 115-130mm, the inner diameter is 80-90mm, and the hollow diameter of the outlet section 11 is 30-50mm; in the cylindrical outlet section 11, the inner layer (i.e. the layer in direct contact with the hollow) is a cerium aluminate carbon layer 12 formed from a paste 1 and having a thickness in the range of 4-6mm, and outside the cerium aluminate carbon layer 12 is a bulk aluminum carbon layer 13 formed from a bulk aluminum carbon layer paste (having a thickness in the range of 20-25 mm), or a slag line zirconium carbon layer 14 formed from a slag line zirconium carbon layer paste (having a thickness in the range of 20-25mm, preferably the same thickness as the bulk aluminum carbon layer 13 of the outlet section 11), wherein the boundary line between the bulk aluminum carbon layer 13 and the slag line zirconium carbon layer 14 is located at a position 120mm from the outlet of the outlet section 11.
3.2 According to the schematic structural diagram of the continuous casting tundish stopper shown in fig. 4, the pug 1 obtained in step (2) and an aluminum carbon layer pug (pug made of brown corundum and crystalline flake graphite) are filled in a mold, and a qualified finished product is finally obtained through the procedures of molding, curing, firing, processing, glazing, X-ray flaw detection and the like, and is named as the continuous casting tundish stopper 1, and the actual physical diagram is shown in fig. 5. According to the schematic structure shown in fig. 4, the stopper rod of the continuous casting tundish is a rod-shaped structure, the length of the stopper rod can be 1200-1800mm, and the stopper rod comprises a rod head 20 at one end and a rod 21 at the other end, wherein the rod head 20 is a cerium aluminate carbon layer 22 formed by pug 1 and positioned at the outer layer, and a first aluminum carbon layer 23 formed by aluminum carbon layer pug and positioned at the inner layer, the rod 21 is a second aluminum carbon layer 24 formed by aluminum carbon layer pug and can be designed into a cylindrical structure (a bulge 26 can be arranged on the outer surface of the cylinder), the outer diameter can be 120-160mm, the stopper rod can also be designed into a hollow or solid structure, a tail hole 25 is arranged at the tail part of the rod 21, a nut is embedded in the tail hole or an internal thread is directly arranged in the tail hole 25, and a connecting rod provided with an external thread matched with the nut or the internal thread in the tail hole 25 can be screwed.
Measuring the volume density and the apparent porosity of the cerium aluminate carbon layer in the functional refractory material according to the national standard GB/T2997-2000; the flexural strength of the cerium aluminate carbon layer in the functional refractory material is measured according to the national standard GB/T3001-2000.
The bulk density, apparent porosity and flexural strength of the cerium aluminate carbon layer in the functional refractory were measured as shown in table 1 below.
Examples 2 to 12
Examples 2 to 12 were carried out according to the procedure of example 1, except that the kind of the rare earth powder used was different, or the molar ratio of the rare earth cerium powder to the aluminum powder was different, or the firing temperature and time were different, specifically:
in the embodiment 2, rare earth lanthanum powder with the purity of more than or equal to 99.0% is used for preparing rare earth raw material 2, the rare earth raw material 2 is used for preparing mud 2, and the mud 2 is used for preparing a continuous casting submerged nozzle 2 and a continuous casting tundish stopper 2 respectively;
in the embodiment 3, rare earth neodymium powder with the purity of more than or equal to 99.0% is used for preparing rare earth raw material 3, the rare earth raw material 3 is used for preparing mud 3, and the mud 3 is used for preparing a continuous casting submerged nozzle 3 and a continuous casting tundish stopper 3 respectively;
in the embodiment 4, rare earth yttrium powder with the purity of more than or equal to 99.0% is used for preparing a rare earth raw material 4, the rare earth raw material 4 is used for preparing a pug 4, and the pug 4 is used for preparing a continuous casting submerged nozzle 4 and a continuous casting tundish stopper 4 respectively;
in the embodiment 5, the rare earth cerium powder with the purity of more than or equal to 99.0% and the aluminum powder with the purity of more than or equal to 99.0% are uniformly mixed according to the molar ratio of Ce to Al of 1.5;
in example 6, rare earth cerium powder having a purity of not less than 99.0% and aluminum powder having a purity of not less than 99.0% are uniformly mixed according to a molar ratio of Ce to Al of 2.
In the embodiment 7, rare earth cerium powder with the purity of not less than 99.0% and aluminum powder with the purity of not less than 99.0% are uniformly mixed according to the molar ratio of Ce to Al of 3;
in the embodiment 8, rare earth cerium powder with the purity of not less than 99.0% and aluminum powder with the purity of not less than 99.0% are uniformly mixed according to the molar ratio of Ce to Al of 0.5;
in example 9, the temperature of the fired intermediate was 1550 ℃ and held for 3.5 hours, and a rare earth raw material 9 was prepared, and a sludge 9 was prepared using the rare earth raw material 9, and a continuous casting submerged nozzle 9 and a continuous casting tundish stopper 9 were prepared from the sludge 9, respectively;
the temperature of the fired intermediate in example 10 was 1650 ℃ and maintained for 4.5 hours, thereby preparing a rare earth raw material 10, and using the rare earth raw material 10 to prepare a sludge 10, a continuous casting submerged entry nozzle 10 and a continuous casting tundish stopper 10 were prepared from the sludge 10, respectively.
In example 11, the temperature of the fired intermediate was 1500 ℃ and held for 3 hours, and a rare earth raw material 11 was prepared, and a sludge 11 was prepared using the rare earth raw material 11, and a continuous casting submerged nozzle 11 and a continuous casting tundish stopper 11 were prepared from the sludge 11, respectively;
in example 12, the temperature of the fired intermediate was 1700 ℃ for 5 hours, and a rare earth raw material 12 was prepared, and a sludge 12 was prepared using the rare earth raw material 12, and a continuous casting submerged nozzle 12 and a continuous casting tundish stopper 12 were prepared from the sludge 12, respectively.
Comparative example 1
Comparative example 1 the procedure of example 1 was followed except that: ceO was mixed according to a molar ratio of Ce to Al of 1 2 And Al 2 O 3 Obtaining an intermediate; the intermediate is fired to obtain a rare earth raw material 13, the rare earth raw material 13 is used to prepare a sludge 13, and the sludge 13 is used to prepare a continuous casting submerged nozzle 13 and a continuous casting tundish stopper 13.
Comparative example 2
Comparative example 2 the procedure of example 1 was followed except that: ceO was mixed according to a molar ratio of Ce to Al of 1 2 And aluminum powder with the purity of more than or equal to 99.0 percent to obtain an intermediate; the intermediate is fired to obtain a rare earth raw material 14, a sludge 14 is prepared from the rare earth raw material 14, and a continuous casting submerged nozzle 14 and a continuous casting tundish stopper 14 are respectively prepared from the sludge 14.
Comparative example 3
Comparative example 3 the procedure of example 1 was followed except that: mixing rare earth cerium powder with the purity of more than or equal to 99.0 percent and Al according to the molar ratio of Ce to Al of 1 2 O 3 Obtaining an intermediate; firing the intermediate to obtain a rare earth raw material 15, preparing a pug 15 by using the rare earth raw material 15, and preparing a continuous casting submerged nozzle 15 and a continuous casting tundish stopper 15 from the pug 15 respectively.
Table 1: rare earth raw materials and refractory materials prepared in examples 1 to 12 and comparative examples 1 to 3
Application example:
in the application example, the U76CrRe rare earth heavy rail steel is produced, the chemical components of the steel are shown in the following table 2, and the specific process route is as follows: KR molten iron pretreatment, converter, LF/VD refining, and a 280X 380mm bloom casting machine.
Table 2: chemical composition of U76CrRe rare earth heavy rail steel (%)
In this application example, 16-furnace U76CrRE rare earth heavy rail steel was co-produced, in which the continuous casting submerged nozzles and continuous casting tundish plugs prepared in the above examples 1 to 12 and comparative examples 1 to 3 were used in the 1 st to 15 th furnaces (application examples 1 to 15), respectively, and the continuous casting submerged nozzle and continuous casting tundish plug having a conventional aluminum-carbon inner layer were used in the 16 th furnace (application example 16). The main technological parameters of continuous casting are shown in the following table 3:
table 3: main technological parameters of continuous casting in production of U76CrRE rare earth heavy rail steel
The reduction of the inner diameter of the continuous casting submerged nozzle after the continuous casting of each furnace steel and the increase of the outer diameter of the position 35mm upwards of the plug rod tip of the continuous casting tundish are measured so as to analyze the influence of each continuous casting submerged nozzle and each continuous casting tundish plug rod on the casting in the continuous casting process. The results are shown in table 4 below and fig. 6. In table 4, the decrease of the inner diameter of the continuous casting submerged nozzle used for each furnace steel and the increase of the thickness of the plug of the continuous casting tundish are described, and fig. 6 shows the decrease of the inner diameter of the continuous casting submerged nozzle of application example 1.
Table 4: inner diameter reduction of continuous casting submerged nozzle used for each furnace steel and thickness increase of continuous casting tundish stopper
As can be seen from the results of table 4 above, when the continuous casting submerged nozzle and the continuous casting tundish stopper prepared in examples 1 to 12 were used in application examples 1 to 12, the decrease in the inner diameter of the continuous casting submerged nozzle and the increase in the outer diameter of the stopper head of the continuous casting tundish were small, wherein the decrease in the inner diameter of the continuous casting submerged nozzle was only 6mm at the maximum, and the increase in the outer diameter of the stopper head of the continuous casting tundish was only 7mm at the maximum, particularly when the alloy consisting of rare earth and Al in a molar ratio of (1-2): 1 when firing the rare earth raw materials of preparation under the 1550-1650 ℃ temperature condition, be more favorable to restraining that package stopper stick head external diameter increases in the middle of continuous casting immersion nozzle internal diameter reduces and continuous casting, wherein continuous casting immersion nozzle internal diameter reduces and is only 4mm at most, package stopper stick head external diameter increases in the middle of the continuous casting is only 5mm at most, when using tombarthite Ce, be further favorable to restraining that package stopper stick head external diameter increases in the middle of continuous casting immersion nozzle internal diameter reduces and the continuous casting, wherein continuous casting immersion nozzle internal diameter reduces and is only 3mm at most, package stopper stick head external diameter increases and is only 3mm at most in the middle of the continuous casting, consequently, can effectively avoid the stopper stick out of control, the mouth of a river blocks up, and then can effectively avoid pouring interruption or production accident in the tombarthite steel production process. And application examples 13 to 15, when the continuous casting submerged nozzle and the continuous casting tundish stopper prepared in comparative examples 1 to 3 were used, respectively, the inner diameter reduction of the continuous casting submerged nozzle and the outer diameter increase of the stopper head of the continuous casting tundish stopper were both large, wherein the inner diameter reduction of the continuous casting submerged nozzle was at least 7mm and at most 8mm, and the outer diameter increase of the stopper head of the continuous casting tundish stopper was at least 8mm and at most 9mm, which easily caused the stopper to be out of control, the nozzle to be blocked, and in severe cases, the casting to be interrupted or the production accident to be caused. In application example 15, a conventional aluminum-carbon inner layer continuous casting submerged nozzle and a conventional aluminum-carbon stopper of a continuous casting tundish, which are easily caused by the plug to be out of control and the nozzle to be blocked, may cause pouring interruption or production accidents under severe conditions.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The composite pug for producing the functional refractory material for steelmaking comprises the following components in percentage by mass: 88 to 92 percent of rare earth raw material, 3 to 5 percent of crystalline flake graphite, 0.5 to 1.5 percent of boron carbide and 4 to 6 percent of phenolic resin;
wherein the rare earth raw material is obtained by the following steps:
1) Mixing rare earth powder with the purity of more than or equal to 99.0 percent and aluminum powder with the purity of more than or equal to 99.0 percent according to the molar ratio of the rare earth to the Al of (0.5-3) to 1 to obtain an intermediate;
2) The intermediate obtained in the step 1) is sintered for 3.5 to 4.5 hours at the temperature of 1500 to 1700 ℃.
2. The composite sludge as claimed in claim 1, wherein the molar ratio of rare earth to Al in step 1) is (1-2): 1.
3. A composite sludge as claimed in claim 1 or 2, wherein in step 2) said temperature is 1550-1650 ℃.
4. The composite sludge as claimed in claim 1 or 2, wherein in step 2) further comprising crushing, sieving and grinding the product obtained by firing to obtain a powder having a particle size of less than 0.5mm, said rare earth raw material being obtained.
5. The composite sludge as claimed in claim 1 or 2, wherein the particle size of the rare earth powder is < 325 mesh and the particle size of the aluminum powder is < 325 mesh in step 1).
6. The composite sludge material according to claim 1 or 2, wherein the rare earth powder comprises rare earth cerium powder, rare earth lanthanum powder, rare earth neodymium powder, rare earth yttrium powder, or a mixture thereof.
7. The composite sludge as claimed in claim 1 or 2, wherein the rare earth powder is rare earth cerium powder.
8. Use of the composite sludge as claimed in any one of claims 1 to 7 for the production of a functional refractory for steel making.
9. The use of claim 8, wherein the steelmaking functional refractory comprises: continuous casting submerged nozzle, continuous casting tundish stopper, retaining wall, brick cup, dam and tundish working layer.
10. A process for the preparation of a composite slip as claimed in any one of claims 1 to 7, which comprises mixing the components of the composite slip in a granulator for a period of from 15 to 30 minutes.
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