CN112778015A - Lightweight periclase-spinel-carbon refractory material and preparation method thereof - Google Patents

Lightweight periclase-spinel-carbon refractory material and preparation method thereof Download PDF

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CN112778015A
CN112778015A CN202110025196.XA CN202110025196A CN112778015A CN 112778015 A CN112778015 A CN 112778015A CN 202110025196 A CN202110025196 A CN 202110025196A CN 112778015 A CN112778015 A CN 112778015A
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spinel
periclase
modified
fine powder
carbon
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CN112778015B (en
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鄢文
刘修毅
陈哲
戴亚洁
李亚伟
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Wuhan University of Science and Engineering WUSE
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Abstract

The invention relates to a lightweight periclase-spinel-carbon refractory material and a preparation method thereof. The technical scheme is as follows: taking 19-28 wt% of modified porous periclase-spinel ceramic particles I and 26-34 wt% of modified porous periclase-spinel ceramic particles II as aggregates, and taking 27-37 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 1-5 wt% of simple substance Si powder and 6-12 wt% of carbon powder as substrates; the method comprises the steps of putting aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-7 wt% of the aggregate and matrix, mixing, adding the matrix, stirring, forming by mechanical pressing, drying, preserving heat at 1390-1610 ℃ in a nitrogen atmosphere, and cooling to obtain the lightweight periclase-spinel-carbon refractory material. The product prepared by the invention has the characteristics of low heat conductivity coefficient, high strength, excellent thermal shock stability, excellent slag resistance and good oxidation resistance, and is suitable for molten steel diversion key devices such as steel tapping holes, sliding plates and the like.

Description

Lightweight periclase-spinel-carbon refractory material and preparation method thereof
Technical Field
The invention belongs to the technical field of lightweight refractory materials. In particular to a lightweight periclase-spinel-carbon refractory material and a preparation method thereof.
Background
Periclase-spinel-carbon refractory materials are widely used in converter, electric furnace lining and tap hole in the steel industry, as well as ladle slag line, etc., and thus are of great interest to those skilled in the art.
Such as the literature technology (Yaohuabai et Al. Al)2O3Influence on slag-erosion resistance of low-carbon magnesia-carbon material non-metal ore, 2019,42(2):80-83) by using fused magnesia and alpha-Al2O3The periclase-spinel-carbon refractory material is prepared by taking metal aluminum powder, silicon powder, graphite, phenolic resin and the like as raw materials, but the adopted fused magnesia is compact aggregate, and alumina and magnesia react at high temperature to generate spinel, so that the product porosity is reduced by a micro-expansion effect generated in the spinel process, the product density is further increased, the product heat conductivity coefficient is high, and energy is wasted.
As for the literature technology (Weizhong, etc., development of metal aluminum combined magnesium-spinel-carbon sliding plates, refractory material, 2007,41(6): 457-.
For another example, the patent technology of 'an ultra-low carbon periclase-spinel-carbon brick for a ladle and a preparation method thereof' (201710216388.2) uses fused magnesia, magnesia-alumina spinel, carbon powder, a bonding agent and an additive as main raw materials, and although the ultra-low carbon periclase-spinel-carbon brick for the ladle is prepared, magnesia-alumina spinel in a product is mainly distributed in a matrix, and the improvement of slag resistance and strength of the product by spinel is limited by the spinel with uneven distribution.
In summary, the prior art still has some disadvantages: firstly, the heat conductivity coefficient is high, so that the heat loss of molten steel is large, and the energy consumption is increased; secondly, the strength and the thermal shock stability of the product are insufficient, so that the refractory material is easy to damage when being repeatedly washed by high-temperature molten steel; thirdly, the slag resistance and the oxidation resistance are insufficient.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a lightweight periclase-spinel-carbon refractory material which is low in heat conductivity coefficient, high in strength, excellent in thermal shock stability, excellent in slag resistance and good in oxidation resistance and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:
step 1, preparation of modified porous periclase-spinel particles and modified porous periclase-spinel fine powder
Step 1.1, heating the aluminum hydroxide fine powder to 340-410 ℃ at the speed of 2-4 ℃/min, preserving the heat for 1-3 h, and cooling to obtain the high-porosity aluminum oxide fine powder.
Step 1.2, placing 10-40 wt% of high-porosity alumina fine powder and 60-90 wt% of light-burned magnesite fine powder in a stirrer, and stirring for 1-3 hours to obtain a mixture I.
Step 1.3, placing the mixture I and the aluminum sol in a stirrer according to the mass ratio of the mixture I to the aluminum sol of 100: 3-6, and stirring for 10-20 min to obtain a mixture II; performing mechanical pressing on the mixture II under the condition of 100-150 MPa, and drying for 18-36 h at the temperature of 110 ℃; and then heating to 1650-1750 ℃ at the speed of 3-5 ℃/min, and preserving the heat for 2-6 h to obtain the micro-nano porous periclase-spinel ceramic with the aperture.
The micro-nano porous periclase-spinel ceramic with the aperture is prepared by the following steps: the apparent porosity is 24-32%; the bulk density is 2.44-2.76 g/cm3(ii) a The compressive strength is 88-192 MPa; the average pore diameter of the pores is 600 nm-1.55 mu m, the pore diameter distribution is double peaks, the small pore peak is 420 nm-820 nm, and the large pore peak is 1.1-2.1 mu m.
Step 1.4, placing the water and the catalyst in a stirrer according to the mass ratio of 100: 0.5-1, and stirring for 6-12 min to obtain a modified solution.
Step 1.5, placing the micro-nano porous periclase-spinel ceramic and the modified solution in a vacuum device according to the mass ratio of 100: 39-44, adding the modified solution, vacuumizing to 2.0-3.0 kPa, standing for 30-60 min, closing a vacuumizing system, naturally drying for 24-32 h, then preserving heat for 12-24 h at 110-150 ℃, and cooling to obtain the modified porous periclase-spinel ceramic.
And step 1.6, crushing and screening the modified porous periclase-spinel ceramic to respectively obtain modified porous periclase-spinel ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous periclase-spinel ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm and modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088 mm.
Step 2, preparation of lightweight periclase-spinel-carbon refractory material
Taking 19-28 wt% of modified porous periclase-spinel ceramic particles I and 26-34 wt% of modified porous periclase-spinel ceramic particles II as aggregates, and taking 27-37 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 1-5 wt% of simple substance Si powder and 6-12 wt% of carbon powder as substrates; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-7 wt% of the aggregate and the matrix, mixing, adding the matrix, uniformly stirring, performing mechanical compression molding under the condition of 120-200 MPa, and drying for 18-36 h at the temperature of 110-130 ℃; finally in N2Partial pressure of 1atm, O2Partial pressure of less than 1.0X 10-14.4Pa and CO partial pressure less than 1.0X 10-6.4And (3) under the atmosphere condition of Pa, heating to 1390-1610 ℃ at the speed of 2-6 ℃/min, preserving the heat for 2-7 h, and naturally cooling to obtain the lightweight periclase-spinel-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: and mixing the liquid thermosetting phenolic resin and nickel nitrate hexahydrate to obtain the modified liquid thermosetting phenolic resin, wherein the mass ratio of the liquid thermosetting phenolic resin to the nickel nitrate hexahydrate is 100: 5-10.
The particle size of the aluminum hydroxide fine powder is less than 88 mu m; al of the aluminum hydroxide fine powder2O3The content is 64-66 wt%.
The particle size of the light-burned magnesite fine powder is less than 44 mu m; the MgO content of the light-burned magnesite fine powder is more than 95 wt%.
The solid content of the aluminum sol is 15-30 wt%; al of the aluminum sol2O3The content is 18 to 42 wt%.
The catalyst is one or two of ferric nitrate nonahydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate3)3·9H2The content of O is more than 98wt percent, and the Co (NO) of the cobalt nitrate hexahydrate3)2·6H2The O content is more than 98 wt%.
The Si content of the simple substance Si powder is more than 98 wt%; the particle size of the simple substance Si powder is less than 45 mu m.
The carbon powder is one or two of crystalline flake graphite and microcrystalline graphite, and the particle size of the carbon powder is less than 74 mu m; wherein: the C content of the crystalline flake graphite is more than 97 wt%, and the C content of the microcrystalline graphite is more than 97 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is more than 40 percent.
Ni (NO) of the nickel nitrate hexahydrate3)2·6H2The O content is more than 98 wt%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
(1) the modified porous periclase-spinel ceramic particles adopted by the invention introduce a micro-nano porous structure, so that the heat conductivity coefficient of the product is effectively reduced.
The invention adopts Al (OH)3The alumina fine powder with high porosity obtained by decomposition is used as a raw material, and the microstructure of the porous periclase-spinel ceramic material is regulated and controlled by utilizing the light-burned magnesite fine powder, alumina sol and high forming pressure, so that modified porous periclase-spinel ceramic particles and modified porous periclase-spinel ceramic fine powder which can be applied to higher temperature and have micro-nano pore size are prepared.
The modified porous periclase-spinel ceramic particles prepared by the invention have a porous structure with more micro-nano pores in the material, can effectively reduce the heat conductivity coefficient of the product, reduce heat loss and save energy.
(2) The micro-nano porous structure adopted by the invention is enhanced by being compounded with the silicon carbide whiskers, the silicon nitride whiskers and the carbon nano tubes which are specially distributed, so that the strength and the thermal shock stability of the product can be effectively improved.
Firstly, the surface of the modified porous periclase-spinel ceramic particle aggregate adopted by the invention is provided with more micro-nano pores, so that the contact surface between the matrix and the aggregate is enlarged, the sintering process of the aggregate and the oxide in the matrix can be accelerated, the interface compatibility of the aggregate and the non-oxide in the matrix can be improved, a sawtooth occlusion-shaped interface is formed, the bonding strength of the aggregate and the matrix is improved, and the strength of the product is improved.
Secondly, the invention further strengthens the strength of the material by utilizing the silicon carbide whiskers and the silicon nitride whiskers which are formed in situ and specially distributed. In the sintering process, because the inside of the aggregate contains a large number of through-shaped micro-nano pores and is attached with the catalyst, under the action of the catalyst, a large number of silicon carbide whiskers, silicon nitride whiskers and carbon nano tubes can be generated among matrix fine powder, inside the aggregate and on an aggregate/matrix sawtooth occlusion-shaped interface structure, the number of whisker bridges at the interface is obviously increased, and an occlusion-interweaving-shaped silicon carbide whisker, silicon nitride whisker and carbon nano tube reinforced interface structure is formed, so that the bonding at the interface is tighter, and the strength of a product is improved.
Thirdly, the invention has a crystal whisker reinforced interface structure of silicon carbide and the like in a meshing-interweaving shape, and can block the crack from expanding along an aggregate/matrix interface and increase the crack expansion resistance under the action of thermal stress. Meanwhile, the micro-nano pore structure contained in the aggregate and the whiskers such as silicon carbide and the like generated in the aggregate can also effectively disperse thermal stress, so that cracks are deflected, the damage caused by the thermal stress is reduced, the thermal shock stability of the product is obviously improved by the action of the micro-nano pore structure and the whiskers such as silicon carbide and the like generated in the aggregate and the occlusion-interweaving whisker reinforced interface structure, and the service life of the product is prolonged.
(3) The special micro-nano pore structure and the silicon carbide whiskers and the silicon nitride whiskers which are specially distributed enable the product to have good slag resistance and oxidation resistance.
Firstly, the silicon carbide whiskers and the silicon nitride whiskers in the occlusion-interweaving state enhance the interface structure, so that the aggregate and the matrix interface are combined more tightly, and the better interface structure prevents the penetration and diffusion of slag and oxygen along the interface, so that the slag resistance and the oxidation resistance of the product are obviously improved.
On the other hand, the smaller the aperture is, the harder the slag is to permeate, the aggregate of the invention contains more micro-nano pores, and the silicon carbide whiskers and the like generated in the pores have poorer wettability with the slag, so the micro-nano pores and the silicon carbide whiskers effectively prevent the slag and oxygen from corroding and permeating under the synergistic action; on the other hand, SiC, Si at the aggregate/matrix interface3N4MgO reacts with oxygen at high temperature to generate forsterite which is beneficial to filling pores on the surface layer of the aggregate, and meanwhile, whiskers such as silicon carbide and the like in the aggregate react with slag at high temperature to increase SiO (silicon oxide) in the permeated slag2The content and the viscosity of the permeated molten slag are increased, and the slag resistance and the oxidation resistance of the product are further improved.
(4) The magnesium aluminate spinel in the invention is distributed more uniformly, which not only can effectively absorb iron ions and manganese ions in the slag, increase the viscosity of the penetrating slag, improve the slag resistance of the product, but also can improve the stress distribution condition between periclase and magnesium aluminate spinel and improve the strength of the product.
The lightweight periclase-spinel-carbon refractory material prepared by the invention is detected as follows: the apparent porosity is 20-28%; the bulk density is 2.38-2.66 g/cm3(ii) a The compressive strength is 51.8 to 83.9 MPa.
Therefore, the lightweight periclase-spinel-carbon refractory material prepared by the invention has the characteristics of low thermal conductivity coefficient, high strength, excellent thermal shock stability, excellent slag resistance and good oxidation resistance, and is suitable for molten steel diversion key devices such as a steel tapping hole, a sliding plate and the like.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope.
A lightweight periclase-spinel-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of modified porous periclase-spinel particles and modified porous periclase-spinel fine powder
Step 1.1, heating the aluminum hydroxide fine powder to 340-410 ℃ at the speed of 2-4 ℃/min, preserving the heat for 1-3 h, and cooling to obtain the high-porosity aluminum oxide fine powder.
Step 1.2, placing 10-40 wt% of high-porosity alumina fine powder and 60-90 wt% of light-burned magnesite fine powder in a stirrer, and stirring for 1-3 hours to obtain a mixture I.
Step 1.3, placing the mixture I and the aluminum sol in a stirrer according to the mass ratio of the mixture I to the aluminum sol of 100: 3-6, and stirring for 10-20 min to obtain a mixture II; performing mechanical pressing on the mixture II under the condition of 100-150 MPa, and drying for 18-36 h at the temperature of 110 ℃; and then heating to 1650-1750 ℃ at the speed of 3-5 ℃/min, and preserving the heat for 2-6 h to obtain the micro-nano porous periclase-spinel ceramic with the aperture.
The micro-nano porous periclase-spinel ceramic with the aperture is prepared by the following steps: the apparent porosity is 24-32%; the bulk density is 2.44-2.76 g/cm3(ii) a The compressive strength is 88-192 MPa; the average pore diameter of the pores is 600 nm-1.55 mu m, the pore diameter distribution is double peaks, the small pore peak is 420 nm-820 nm, and the large pore peak is 1.1-2.1 mu m.
Step 1.4, placing the water and the catalyst in a stirrer according to the mass ratio of 100: 0.5-1, and stirring for 6-12 min to obtain a modified solution.
Step 1.5, placing the micro-nano porous periclase-spinel ceramic and the modified solution in a vacuum device according to the mass ratio of 100: 39-44, adding the modified solution, vacuumizing to 2.0-3.0 kPa, standing for 30-60 min, closing a vacuumizing system, naturally drying for 24-32 h, then preserving heat for 12-24 h at 110-150 ℃, and cooling to obtain the modified porous periclase-spinel ceramic.
And step 1.6, crushing and screening the modified porous periclase-spinel ceramic to respectively obtain modified porous periclase-spinel ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous periclase-spinel ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm and modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088 mm.
Step 2, preparation of lightweight periclase-spinel-carbon refractory material
Taking 19-28 wt% of modified porous periclase-spinel ceramic particles I and 26-34 wt% of modified porous periclase-spinel ceramic particles II as aggregates, and taking 27-37 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 1-5 wt% of simple substance Si powder and 6-12 wt% of carbon powder as substrates; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-7 wt% of the aggregate and the matrix, mixing, adding the matrix, uniformly stirring, performing mechanical compression molding under the condition of 120-200 MPa, and drying for 18-36 h at the temperature of 110-130 ℃; finally in N2Partial pressure of 1atm, O2Partial pressure of less than 1.0X 10-14.4Pa and CO partial pressure less than 1.0X 10-6.4And (3) under the atmosphere condition of Pa, heating to 1390-1610 ℃ at the speed of 2-6 ℃/min, preserving the heat for 2-7 h, and naturally cooling to obtain the lightweight periclase-spinel-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: and mixing the liquid thermosetting phenolic resin and nickel nitrate hexahydrate to obtain the modified liquid thermosetting phenolic resin, wherein the mass ratio of the liquid thermosetting phenolic resin to the nickel nitrate hexahydrate is 100: 5-10.
Al of the aluminum hydroxide fine powder2O3The content is 64-66 wt%.
The MgO content of the light-burned magnesite fine powder is more than 95 wt%.
The solid content of the aluminum sol is 15-30 wt%; al of the aluminum sol2O3The content is 18 to 42 wt%.
The catalyst is nineOne or two of ferric nitrate hydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate3)3·9H2The content of O is more than 98wt percent, and the Co (NO) of the cobalt nitrate hexahydrate3)2·6H2The O content is more than 98 wt%.
The Si content of the simple substance Si powder is more than 98 wt%.
The carbon powder is one or two of crystalline flake graphite and microcrystalline graphite; wherein: the C content of the crystalline flake graphite is more than 97 wt%, and the C content of the microcrystalline graphite is more than 97 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is more than 40 percent.
Ni (NO) of the nickel nitrate hexahydrate3)2·6H2The O content is more than 98 wt%.
In this embodiment:
the particle size of the aluminum hydroxide fine powder is less than 88 mu m;
the particle size of the light-burned magnesite fine powder is less than 44 mu m;
the particle size of the simple substance Si powder is less than 45 mu m;
the grain size of the carbon powder is less than 74 mu m.
The detailed description is omitted in the embodiments.
Example 1
A lightweight periclase-spinel-carbon refractory material and a preparation method thereof. The preparation method of this example:
step 1.1, heating the aluminum hydroxide fine powder to 390 ℃ at the speed of 4 ℃/min, preserving the heat for 2.5h, and cooling to obtain the alumina fine powder with high porosity.
Step 1.2, placing 10 wt% of high-porosity alumina fine powder and 90 wt% of light-burned magnesite fine powder in a stirrer, and stirring for 2 hours to obtain a mixture I.
Step 1.3, placing the mixture I and the aluminum sol in a stirrer according to the mass ratio of the mixture I to the aluminum sol of 100: 5, and stirring for 20min to obtain a mixture II; performing mechanical pressing on the mixture II under the condition of 135MPa, and drying for 30h at the temperature of 110 ℃; and then the temperature is raised to 1750 ℃ at the speed of 4 ℃/min, and the temperature is preserved for 4.5 hours, thus obtaining the micro-nano porous periclase-spinel ceramic.
The micro-nano porous periclase-spinel ceramic with the aperture is prepared by the following steps: the apparent porosity is 29.0%; the bulk density is 2.60g/cm3(ii) a The compressive strength is 90 MPa; the average pore diameter of pores is 1.23 μm, the pore diameter distribution is bimodal, the small pore peak is 430nm, and the large pore peak is 2.08 μm.
And step 1.4, placing the water and the catalyst in a stirrer according to the mass ratio of 100: 0.5 of the water to the catalyst, and stirring for 10min to obtain a modified solution.
Step 1.5, according to the mass ratio of the micro-nano-aperture porous periclase-spinel ceramic to the modified solution being 100: 39, firstly placing the micro-nano-aperture porous periclase-spinel ceramic in a vacuum device, then adding the modified solution, vacuumizing to 2.7kPa, standing for 50min, closing a vacuumizing system, naturally drying for 29h, then preserving heat for 24h at 135 ℃, and cooling to obtain the modified porous periclase-spinel ceramic.
And step 1.6, crushing and screening the modified porous periclase-spinel ceramic to respectively obtain modified porous periclase-spinel ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous periclase-spinel ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm and modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088 mm.
Step 2, preparation of lightweight periclase-spinel-carbon refractory material
19.4 wt% of modified porous periclase-spinel ceramic particles I and 34 wt% of modified porous periclase-spinel ceramic particles II are used as aggregates, 35.3 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 5 wt% of simple substance Si powder and 6.3 wt% of carbon powder are used as matrixes; firstly, placing the aggregate into a stirrer, then adding modified liquid thermosetting phenolic resin which accounts for 7 wt% of the sum of the aggregate and the matrix, mixing, then adding the matrix, uniformly stirring, carrying out mechanical compression molding under the condition of 180MPa, and drying for 36 hours at the temperature of 115 ℃; finally in N2Partial pressure of 1atm, O2Partial pressure of less than 1.0X 10-14.4Pa and CO partial pressure less than 1.0X 10-6.4Atmospheric condition of PaAnd then, heating to 1610 ℃ at the speed of 5 ℃/min, preserving the heat for 6 hours, and naturally cooling to obtain the lightweight periclase-spinel-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: and mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of the liquid thermosetting phenolic resin to the nickel nitrate hexahydrate of 100: 6 to obtain the modified liquid thermosetting phenolic resin.
Al of the aluminum hydroxide fine powder2O3The content was 64 wt%.
The MgO content of the light-burned magnesite fine powder is 95.1 wt%.
The solid content of the aluminum sol is 19 wt%; al of the aluminum sol2O3The content was 29 wt%.
The catalyst is a mixture of ferric nitrate nonahydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate3)3·9H2The content of O is 98.1 wt%, and the Co (NO) of the cobalt nitrate hexahydrate3)2·6H2The O content was 98.9 wt%.
The Si content of the simple substance Si powder is 98.2 wt%.
The carbon powder is crystalline flake graphite; the C content of the crystalline flake graphite is 97.6 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 41%.
Ni (NO) of the nickel nitrate hexahydrate3)2·6H2The O content was 98.3 wt%.
The lightweight periclase-spinel-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 20.2%; the bulk density is 2.64g/cm3(ii) a The compressive strength was 74.9 MPa.
Example 2
A lightweight periclase-spinel-carbon refractory material and a preparation method thereof. The preparation method of this example:
step 1, preparation of modified porous periclase-spinel particles and modified porous periclase-spinel fine powder
Step 1.1, heating the aluminum hydroxide fine powder to 340 ℃ at the speed of 3 ℃/min, preserving the heat for 1h, and cooling to obtain the high-porosity aluminum oxide fine powder.
Step 1.2, placing 30 wt% of high-porosity alumina fine powder and 70 wt% of light-burned magnesite fine powder in a stirrer, and stirring for 1h to obtain a mixture I.
Step 1.3, placing the mixture I and the aluminum sol in a stirrer according to the mass ratio of the mixture I to the aluminum sol of 100: 3, and stirring for 17min to obtain a mixture II; performing mechanical pressing on the mixture II under the condition of 150MPa, and drying for 18h at the temperature of 110 ℃; and then heating to 1720 ℃ at the speed of 3 ℃/min, and preserving heat for 6h to obtain the micro-nano porous periclase-spinel ceramic.
The micro-nano porous periclase-spinel ceramic with the aperture is prepared by the following steps: the apparent porosity is 27.3%; the bulk density is 2.68g/cm3(ii) a The compressive strength is 190 MPa; the average pore diameter of pores is 970nm, the pore diameter distribution is double peaks, the small pore peak is 810nm, and the large pore peak is 1.12 μm.
And step 1.4, placing the water and the catalyst in a stirrer according to the mass ratio of 100: 0.8 of the water to the catalyst, and stirring for 8min to obtain a modified solution.
Step 1.5, according to the mass ratio of the micro-nano-aperture porous periclase-spinel ceramic to the modified solution being 100: 44, firstly placing the micro-nano-aperture porous periclase-spinel ceramic in a vacuum device, then adding the modified solution, vacuumizing to 2.4kPa, standing for 40min, closing a vacuumizing system, naturally drying for 24h, then preserving heat for 12h at 150 ℃, and cooling to obtain the modified porous periclase-spinel ceramic.
And step 1.6, crushing and screening the modified porous periclase-spinel ceramic to respectively obtain modified porous periclase-spinel ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous periclase-spinel ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm and modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088 mm.
Step 2, preparation of lightweight periclase-spinel-carbon refractory material
Modified porosity at 23.9 wt%The method comprises the following steps of taking periclase-spinel ceramic particles I and 26 wt% of modified porous periclase-spinel ceramic particles II as aggregates, and taking 37 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 2.7 wt% of simple substance Si powder and 10.4 wt% of carbon powder as matrixes; firstly, placing the aggregate into a stirrer, then adding modified liquid thermosetting phenolic resin accounting for 4 wt% of the sum of the aggregate and the matrix, mixing, then adding the matrix, uniformly stirring, carrying out mechanical compression molding under the condition of 120MPa, and drying for 24 hours at the temperature of 130 ℃; finally in N2Partial pressure of 1atm, O2Partial pressure of less than 1.0X 10-14.4Pa and CO partial pressure less than 1.0X 10-6.4And (3) heating to 1390 ℃ at the speed of 3.5 ℃/min under the atmosphere condition of Pa, preserving heat for 4h, and naturally cooling to prepare the lightweight periclase-spinel-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: and mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of the liquid thermosetting phenolic resin to the nickel nitrate hexahydrate of 100: 5 to obtain the modified liquid thermosetting phenolic resin.
Al of the aluminum hydroxide fine powder2O3The content was 64.5 wt%.
The MgO content of the light-burned magnesite fine powder is 96 wt%.
The solid content of the aluminum sol is 15 wt%; al of the aluminum sol2O3The content was 42 wt%.
The catalyst is ferric nitrate nonahydrate; fe (NO) of the iron nitrate nonahydrate3)3·9H2The O content was 98.2 wt%.
The Si content of the simple substance Si powder is 98.4 wt%.
The carbon powder is a mixture of crystalline flake graphite and microcrystalline graphite; wherein: the content of C in the crystalline flake graphite is 97.9 wt%, and the content of C in the microcrystalline graphite is 97.2 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 42%.
Ni (NO) of the nickel nitrate hexahydrate3)2·6H2The O content was 98.7 wt%.
The lightweight periclase-spinel-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 23.4%; the bulk density is 2.56g/cm3(ii) a The compressive strength was 52.0 MPa.
Example 3
A lightweight periclase-spinel-carbon refractory material and a preparation method thereof. The preparation method of this example:
step 1, preparation of modified porous periclase-spinel particles and modified porous periclase-spinel fine powder
Step 1.1, heating the aluminum hydroxide fine powder to 360 ℃ at the speed of 2 ℃/min, preserving the heat for 3h, and cooling to obtain the high-porosity aluminum oxide fine powder.
Step 1.2, placing 20 wt% of high-porosity alumina fine powder and 80 wt% of light-burned magnesite fine powder in a stirrer, and stirring for 3 hours to obtain a mixture I.
Step 1.3, placing the mixture I and the aluminum sol in a stirrer according to the mass ratio of the mixture I to the aluminum sol of 100: 4, and stirring for 14min to obtain a mixture II; performing mechanical pressing on the mixture II under the condition of 100MPa, and drying for 36h at the temperature of 110 ℃; and then heating to 1650 ℃ at the speed of 3.5 ℃/min, and preserving the heat for 3h to obtain the micro-nano porous periclase-spinel ceramic.
The micro-nano porous periclase-spinel ceramic with the aperture is prepared by the following steps: apparent porosity was 31.7%; the bulk density is 2.49g/cm3(ii) a The compressive strength is 129 MPa; the average pore diameter of pores is 1.54 μm, the pore diameter distribution is bimodal, the small pore peak is 680nm, and the large pore peak is 1.81 μm.
And step 1.4, placing the water and the catalyst in a stirrer according to the mass ratio of 100: 1 of the water to the catalyst, and stirring for 6min to obtain a modified solution.
Step 1.5, according to the mass ratio of the micro-nano-aperture porous periclase-spinel ceramic to the modified solution being 100: 41, firstly placing the micro-nano-aperture porous periclase-spinel ceramic in a vacuum device, adding the modified solution, vacuumizing to 3.0kPa, standing for 30min, closing a vacuumizing system, naturally drying for 32h, then preserving heat for 16h at 110 ℃, and cooling to obtain the modified porous periclase-spinel ceramic.
And step 1.6, crushing and screening the modified porous periclase-spinel ceramic to respectively obtain modified porous periclase-spinel ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous periclase-spinel ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm and modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088 mm.
Step 2, preparation of lightweight periclase-spinel-carbon refractory material
26.2 wt% of modified porous periclase-spinel ceramic particles I and 28.8 wt% of modified porous periclase-spinel ceramic particles II are used as aggregates, and 31.9 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 1.1 wt% of simple substance Si powder and 12 wt% of carbon powder are used as matrixes; firstly, placing the aggregate into a stirrer, then adding modified liquid thermosetting phenolic resin accounting for 2 wt% of the sum of the aggregate and the matrix, mixing, then adding the matrix, uniformly stirring, carrying out mechanical compression molding under the condition of 150MPa, and drying for 18h at the temperature of 110 ℃; finally in N2Partial pressure of 1atm, O2Partial pressure of less than 1.0X 10-14.4Pa and CO partial pressure less than 1.0X 10-6.4And (3) under the atmosphere condition of Pa, heating to 1450 ℃ at the speed of 2 ℃/min, preserving the heat for 7h, and naturally cooling to prepare the lightweight periclase-spinel-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: and mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of the liquid thermosetting phenolic resin to the nickel nitrate hexahydrate of 100: 10 to obtain the modified liquid thermosetting phenolic resin.
Al of the aluminum hydroxide fine powder2O3The content was 65 wt%.
The MgO content of the light-burned magnesite fine powder is 95.6 wt%.
The solid content of the aluminum sol is 24 wt%; al of the aluminum sol2O3The content was 18 wt%.
The catalyst is a mixture of ferric nitrate nonahydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate3)3·9H2The content of O is 98.4 wt%, and the Co (NO) of the cobalt nitrate hexahydrate3)2·6H2The O content was 98.7 wt%.
The Si content of the simple substance Si powder is 98.3 wt%.
The carbon powder is crystalline flake graphite; the C content of the flake graphite is 97.4 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 44%.
Ni (NO) of the nickel nitrate hexahydrate3)2·6H2The O content was 98.5 wt%.
The lightweight periclase-spinel-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 27.8%; the bulk density is 2.39g/cm3(ii) a The compressive strength was 68.1 MPa.
Example 4
A lightweight periclase-spinel-carbon refractory material and a preparation method thereof. The preparation method of this example:
step 1, preparation of modified porous periclase-spinel particles and modified porous periclase-spinel fine powder
Step 1.1, heating the aluminum hydroxide fine powder to 410 ℃ at the speed of 2.5 ℃/min, preserving the heat for 2h, and cooling to obtain the high-porosity aluminum oxide fine powder.
Step 1.2, placing 40 wt% of high-porosity alumina fine powder and 60 wt% of light-burned magnesite fine powder in a stirrer, and stirring for 2.5 hours to obtain a mixture I.
Step 1.3, placing the mixture I and the aluminum sol in a stirrer according to the mass ratio of the mixture I to the aluminum sol of 100: 6, and stirring for 10min to obtain a mixture II; performing mechanical pressing molding on the mixture II under the condition of 120MPa, and drying for 24 hours at the temperature of 110 ℃; and then heating to 1680 ℃ at the speed of 5 ℃/min, and preserving the heat for 2 hours to obtain the micro-nano porous periclase-spinel ceramic.
The micro-nano porous periclase-spinel ceramic with the aperture is prepared by the following steps: the apparent porosity is 24.5%; the bulk density is 2.74g/cm3(ii) a The compressive strength is 156 MPa; average pore diameter of pores of610nm, double peaks in pore size distribution, 520nm in small pore peak and 1.48 μm in large pore peak.
Step 1.4, placing the water and the catalyst in a stirrer according to the mass ratio of 100: 0.7 of the water to the catalyst, and stirring for 12min to obtain a modified solution.
Step 1.5, according to the mass ratio of the micro-nano-aperture porous periclase-spinel ceramic to the modified solution being 100: 42, firstly placing the micro-nano-aperture porous periclase-spinel ceramic in a vacuum device, then adding the modified solution, vacuumizing to 2.0kPa, standing for 60min, closing a vacuumizing system, naturally drying for 27h, then preserving heat for 21h at 125 ℃, and cooling to obtain the modified porous periclase-spinel ceramic.
And step 1.6, crushing and screening the modified porous periclase-spinel ceramic to respectively obtain modified porous periclase-spinel ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous periclase-spinel ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm and modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088 mm.
Step 2, preparation of lightweight periclase-spinel-carbon refractory material
28 wt% of modified porous periclase-spinel ceramic particles I and 31.7 wt% of modified porous periclase-spinel ceramic particles II are used as aggregates, and 27 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 4.3 wt% of simple substance Si powder and 9 wt% of carbon powder are used as matrixes; firstly, placing the aggregate into a stirrer, then adding modified liquid thermosetting phenolic resin accounting for 6 wt% of the sum of the aggregate and the matrix, mixing, then adding the matrix, uniformly stirring, carrying out mechanical compression molding under the condition of 200MPa, and drying for 30 hours at the temperature of 120 ℃; finally in N2Partial pressure of 1atm, O2Partial pressure of less than 1.0X 10-14.4Pa and CO partial pressure less than 1.0X 10-6.4And (3) under the atmosphere condition of Pa, heating to 1530 ℃ at the speed of 6 ℃/min, preserving the heat for 2h, and naturally cooling to obtain the lightweight periclase-spinel-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: and mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of the liquid thermosetting phenolic resin to the nickel nitrate hexahydrate of 100: 8 to obtain the modified liquid thermosetting phenolic resin.
Al of the aluminum hydroxide fine powder2O3The content was 66 wt%.
The MgO content of the light-burned magnesite fine powder is 95.3 wt%.
The solid content of the aluminum sol is 30 wt%; al of the aluminum sol2O3The content was 34 wt%.
The catalyst is cobalt nitrate hexahydrate; co (NO) of the cobalt nitrate hexahydrate3)2·6H2The O content was 98.1 wt%.
The Si content of the simple substance Si powder is 98.1 wt%.
The carbon powder is microcrystalline graphite; the content of C in the microcrystalline graphite is 97.5 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 43 percent.
Ni (NO) of the nickel nitrate hexahydrate3)2·6H2The O content was 98.9 wt%.
The lightweight periclase-spinel-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 26.1%; the bulk density is 2.45g/cm3(ii) a The compressive strength was 83.7 MPa.
Compared with the prior art, the specific implementation mode has the following positive effects:
(1) the modified porous periclase-spinel ceramic particles adopted by the specific embodiment introduce a micro-nano porous structure, so that the heat conductivity coefficient of the product is effectively reduced.
The specific embodiment adopts Al (OH)3The alumina fine powder with high porosity obtained by decomposition is used as a raw material, and the microstructure of the porous periclase-spinel ceramic material is regulated and controlled by utilizing the light-burned magnesite fine powder, alumina sol and high forming pressure, so that modified porous periclase-spinel ceramic particles and modified porous periclase-spinel ceramic fine powder which can be applied to higher temperature and have micro-nano pore size are prepared.
The modified porous periclase-spinel ceramic particles prepared by the embodiment enable the interior of the material to have a porous structure with more micro-nano holes, can effectively reduce the heat conductivity coefficient of the product, reduce heat loss and save energy.
(2) The micro-nano porous structure adopted by the specific embodiment is enhanced by being compounded with the silicon carbide whiskers, the silicon nitride whiskers and the carbon nano tubes which are specially distributed, so that the strength and the thermal shock stability of the product can be effectively improved.
Firstly, the surface of the modified porous periclase-spinel ceramic particle aggregate adopted by the embodiment has more micro-nano pores, so that the contact surface between the matrix and the aggregate is enlarged, the sintering process of the aggregate and the oxide in the matrix can be accelerated, the interface compatibility of the aggregate and the non-oxide in the matrix can be improved, a sawtooth occlusion-shaped interface is formed, the bonding strength of the aggregate and the matrix is improved, and the strength of a product is improved.
Secondly, the specific embodiment further strengthens the material strength by using the silicon carbide whiskers and the silicon nitride whiskers which are formed in situ and specially distributed. In the sintering process, because the inside of the aggregate contains a large number of through-shaped micro-nano pores and is attached with the catalyst, under the action of the catalyst, a large number of silicon carbide whiskers, silicon nitride whiskers and carbon nano tubes can be generated among matrix fine powder, inside the aggregate and on an aggregate/matrix sawtooth occlusion-shaped interface structure, the number of whisker bridges at the interface is obviously increased, and an occlusion-interweaving-shaped silicon carbide whisker, silicon nitride whisker and carbon nano tube reinforced interface structure is formed, so that the bonding at the interface is tighter, and the strength of a product is improved.
Thirdly, the specific embodiment has a whisker reinforced interface structure such as silicon carbide in a meshing-interweaving shape, and the like, and can block the crack from expanding along the interface of the aggregate/matrix when the specific embodiment is subjected to the action of thermal stress, so that the crack expansion resistance is increased. Meanwhile, the micro-nano pore structure contained in the aggregate and the whiskers such as silicon carbide and the like generated in the aggregate can also effectively disperse thermal stress, so that cracks are deflected, the damage caused by the thermal stress is reduced, the thermal shock stability of the product is obviously improved by the action of the micro-nano pore structure and the whiskers such as silicon carbide and the like generated in the aggregate and the occlusion-interweaving whisker reinforced interface structure, and the service life of the product is prolonged.
(3) The special micro-nano pore structure and the silicon carbide whiskers and the silicon nitride whiskers which are specially distributed enable the product to have good slag resistance and oxidation resistance.
Firstly, the silicon carbide whiskers and the silicon nitride whiskers in the occlusion-interweaving state enhance the interface structure, so that the aggregate and the matrix interface are combined more tightly, and the better interface structure prevents the penetration and diffusion of slag and oxygen along the interface, so that the slag resistance and the oxidation resistance of the product are obviously improved.
On the other hand, the smaller the pore diameter is, the harder the slag is to permeate, the aggregate of the embodiment contains more micro-nano pores, and the silicon carbide whiskers and the like generated in the pores have poorer wettability with the slag, so that the micro-nano pores and the silicon carbide whiskers effectively prevent the slag and oxygen from corroding and permeating under the synergistic action; on the other hand, SiC, Si at the aggregate/matrix interface3N4MgO reacts with oxygen at high temperature to generate forsterite which is beneficial to filling pores on the surface layer of the aggregate, and meanwhile, whiskers such as silicon carbide and the like in the aggregate react with slag at high temperature to increase SiO (silicon oxide) in the permeated slag2The content and the viscosity of the permeated molten slag are increased, and the slag resistance and the oxidation resistance of the product are further improved.
(4) The magnesium aluminate spinel in the specific embodiment is more uniformly distributed, so that iron ions and manganese ions in molten slag can be more effectively absorbed, the viscosity of the molten slag is increased, the slag resistance of the obtained product is improved, the stress distribution condition between periclase and magnesium aluminate spinel can be improved, and the strength of the product is improved.
The lightweight periclase-spinel-carbon refractory material prepared by the specific embodiment is detected as follows: the apparent porosity is 20-28%; the bulk density is 2.38-2.66 g/cm3(ii) a The compressive strength is 51.8 to 83.9 MPa.
Therefore, the lightweight periclase-spinel-carbon refractory material prepared by the embodiment has the characteristics of low thermal conductivity, high strength, excellent thermal shock stability, excellent slag resistance and good oxidation resistance, and is suitable for molten steel diversion key devices such as a steel tapping hole, a sliding plate and the like.

Claims (10)

1. A preparation method of a lightweight periclase-spinel-carbon refractory material is characterized by comprising the following steps:
step 1, preparation of modified porous periclase-spinel particles and modified porous periclase-spinel fine powder
Step 1.1, heating the aluminum hydroxide fine powder to 340-410 ℃ at the speed of 2-4 ℃/min, preserving the heat for 1-3 h, and cooling to obtain high-porosity aluminum oxide fine powder;
step 1.2, placing 10-40 wt% of high-porosity alumina fine powder and 60-90 wt% of light-burned magnesite fine powder in a stirrer, and stirring for 1-3 hours to obtain a mixture I;
step 1.3, placing the mixture I and the aluminum sol in a stirrer according to the mass ratio of the mixture I to the aluminum sol of 100: 3-6, and stirring for 10-20 min to obtain a mixture II; performing mechanical pressing on the mixture II under the condition of 100-150 MPa, and drying for 18-36 h at the temperature of 110 ℃; heating to 1650-1750 ℃ at the speed of 3-5 ℃/min, and preserving the heat for 2-6 h to obtain the micro-nano porous periclase-spinel ceramic with the aperture;
the micro-nano porous periclase-spinel ceramic with the aperture is prepared by the following steps: the apparent porosity is 24-32%; the bulk density is 2.44-2.76 g/cm3(ii) a The compressive strength is 88-192 MPa; the average pore diameter of the pores is 600 nm-1.55 mu m, the pore diameter distribution is double peaks, the small pore peak is 420 nm-820 nm, and the large pore peak is 1.1-2.1 mu m;
step 1.4, placing the water and the catalyst in a stirrer according to the mass ratio of 100: 0.5-1, and stirring for 6-12 min to obtain a modified solution;
step 1.5, placing the micro-nano porous periclase-spinel ceramic and a modified solution in a vacuum device according to the mass ratio of 100: 39-44, adding the modified solution, vacuumizing to 2.0-3.0 kPa, standing for 30-60 min, closing a vacuumizing system, naturally drying for 24-32 h, then preserving heat for 12-24 h at 110-150 ℃, and cooling to obtain the modified porous periclase-spinel ceramic;
step 1.6, crushing and screening the modified porous periclase-spinel ceramic to respectively obtain modified porous periclase-spinel ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous periclase-spinel ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm and modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088 mm;
step 2, preparation of lightweight periclase-spinel-carbon refractory material
Taking 19-28 wt% of modified porous periclase-spinel ceramic particles I and 26-34 wt% of modified porous periclase-spinel ceramic particles II as aggregates, and taking 27-37 wt% of modified porous periclase-spinel ceramic fine powder with the particle size of less than 0.088mm, 1-5 wt% of simple substance Si powder and 6-12 wt% of carbon powder as substrates; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-7 wt% of the aggregate and the matrix, mixing, adding the matrix, uniformly stirring, performing mechanical compression molding under the condition of 120-200 MPa, and drying for 18-36 h at the temperature of 110-130 ℃; finally in N2Partial pressure of 1atm, O2Partial pressure of less than 1.0X 10-14.4Pa and CO partial pressure less than 1.0X 10-6.4Heating to 1390-1610 ℃ at the speed of 2-6 ℃/min under the atmosphere condition of Pa, preserving the heat for 2-7 h, and naturally cooling to prepare the lightweight periclase-spinel-carbon refractory material;
the preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: and mixing the liquid thermosetting phenolic resin and nickel nitrate hexahydrate to obtain the modified liquid thermosetting phenolic resin, wherein the mass ratio of the liquid thermosetting phenolic resin to the nickel nitrate hexahydrate is 100: 5-10.
2. The method of producing a lightweight periclase-spinel-carbon refractory of claim 1, wherein the fine aluminum hydroxide powder has a particle size of < 88 μm; al of the aluminum hydroxide fine powder2O3The content is 64-66 wt%.
3. The method of making a lightweight periclase-spinel-carbon refractory of claim 1, wherein the light-burned magnesite fines have a particle size < 44 μ ι η; the MgO content of the light-burned magnesite fine powder is more than 95 wt%.
4. The method for preparing a lightweight periclase-spinel-carbon refractory according to claim 1, wherein the alumina sol has a solid content of 15 to 30 wt%; al of the aluminum sol2O3The content is 18 to 42 wt%.
5. The method of preparing a lightweight periclase-spinel-carbon refractory according to claim 1, wherein the catalyst is one or both of iron nitrate nonahydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate3)3·9H2The content of O is more than 98wt percent, and the Co (NO) of the cobalt nitrate hexahydrate3)2·6H2The O content is more than 98 wt%.
6. The method of making a lightweight periclase-spinel-carbon refractory of claim 1, wherein the elemental Si powder has a Si content > 98 wt%; the particle size of the simple substance Si powder is less than 45 mu m.
7. The method for preparing a lightweight periclase-spinel-carbon refractory according to claim 1, wherein the carbon powder is one or both of crystalline flake graphite and microcrystalline graphite, and the particle size of the carbon powder is < 74 μm; wherein: the C content of the crystalline flake graphite is more than 97 wt%, and the C content of the microcrystalline graphite is more than 97 wt%.
8. The method of producing a lightweight periclase-spinel-carbon refractory of claim 1, wherein the liquid thermosetting phenol resin has a carbon residue ratio of > 40%.
9. The method of producing a lightweight periclase-spinel-carbon refractory of claim 1, wherein the N of nickel nitrate hexahydratei(NO3)2·6H2The O content is more than 98 wt%.
10. A lightweight periclase-spinel-carbon refractory, characterized in that the lightweight periclase-spinel-carbon refractory is prepared by the method of preparing a lightweight periclase-spinel-carbon refractory according to claims 1 to 9.
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