WO2022237727A1 - 耐蚀损性耐火材料、制备方法及其应用 - Google Patents

耐蚀损性耐火材料、制备方法及其应用 Download PDF

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WO2022237727A1
WO2022237727A1 PCT/CN2022/091728 CN2022091728W WO2022237727A1 WO 2022237727 A1 WO2022237727 A1 WO 2022237727A1 CN 2022091728 W CN2022091728 W CN 2022091728W WO 2022237727 A1 WO2022237727 A1 WO 2022237727A1
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Prior art keywords
fine powder
corundum
refractory material
cao
powder
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PCT/CN2022/091728
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English (en)
French (fr)
Inventor
陈俊红
封吉圣
贾元平
李斌
朱波
李广奇
郭玉涛
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Zibo City Luzhong Refractories Co Ltd
Zibo Langfeng High Temperature Materials Co Ltd
University of Science and Technology Beijing USTB
Original Assignee
Zibo City Luzhong Refractories Co Ltd
Zibo Langfeng High Temperature Materials Co Ltd
University of Science and Technology Beijing USTB
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Application filed by Zibo City Luzhong Refractories Co Ltd, Zibo Langfeng High Temperature Materials Co Ltd, University of Science and Technology Beijing USTB filed Critical Zibo City Luzhong Refractories Co Ltd
Priority to EP22806690.8A priority Critical patent/EP4339175A4/en
Priority to KR1020237042548A priority patent/KR20240051885A/ko
Priority to US18/290,388 priority patent/US20240246862A1/en
Priority to JP2023569898A priority patent/JP7774814B2/ja
Publication of WO2022237727A1 publication Critical patent/WO2022237727A1/zh
Anticipated expiration legal-status Critical
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Definitions

  • the invention relates to the technical field of refractory materials, in particular to a high-corrosion-resistant refractory material, a preparation method and an application thereof.
  • the molten steel After the molten iron is blown by the converter, due to the presence of more oxygen, the molten steel must go through the refining process, that is, mainly deoxidation, desulfurization and removal of non-metallic inclusions, etc.; this process generally requires higher temperature and higher slag alkalinity. Damage to refractory materials during the refining process is very serious, mainly due to high temperature and high alkalinity slag.
  • the working lining used for refining ladles is generally a relatively good refractory material.
  • the purity of the raw material is high and the corrosion resistance is good, such as corundum currently used -The main raw material of spinel castable, corundum-MgO- SiO2 castable, etc. is corundum.
  • the basicity of refining slag is generally high and the viscosity is low. This is mainly for desulfurization and changing the properties of inclusions, etc., but this also leads to deep penetration of slag in refractory materials, and penetration means refractory material deterioration and erosion. Due to the large difference in expansion coefficient and high temperature performance between the metamorphic layer and the original brick layer, the refractory material will be peeled off and damaged, which is a very fatal damage method for the refractory material.
  • Refractory materials are different from ceramics. In the application of refractory materials, there are generally large temperature changes and large thermal stress. Therefore, in order to avoid stress cracking and damage of refractory materials during use, certain pores need to be reserved in refractory materials. rate to buffer the stress of expansion, such as corundum-spinel castables, which retain 15-19% of the porosity; these pores also provide convenient conditions for the infiltration of low-viscosity slag while buffering the expansion stress, resulting in infiltration and peeling damage. For the existing refractory material preparation technology and research concept, it is necessary to retain certain pores. The fundamental reason is to avoid stress damage of refractory materials and ensure thermal shock stability.
  • refractory materials used in ladles need to meet three points: corrosion resistance, penetration resistance and thermal shock resistance, and thermal shock stability, penetration resistance, and erosion resistance are contradictory.
  • Magnesia-carbon bricks and alumina-magnesia-carbon bricks are currently the first major type of ladle lining materials used in industrial applications.
  • the idea is to prepare them by adding graphite based on magnesia and corundum with good corrosion resistance. Due to the low wettability of graphite, it prevents slag and molten steel from penetrating into the refractory material. At the same time, based on the high thermal conductivity of graphite, the temperature gradient inside the refractory material is reduced, the thermal stress caused by the sudden temperature change is improved, and the refractory material is improved. Thermal shock stability.
  • graphite materials have the problem of adding carbon to steel during use, especially when smelting ultra-low carbon steel.
  • the oxidation of graphite also leads to accelerated damage of such materials, because graphite oxidation is equivalent to increasing pores. Carbonization of refined ladle refractories is an important development direction.
  • Corundum-spinel or corundum-MgO-SiO 2 system castables are carbon-free refractory materials currently used in industrial applications.
  • the raw materials of this type of castable are high-purity and high-corrosion-resistant raw materials, but the refractory materials constructed together have thermal shock stability, permeability resistance, and erosion resistance. contradictions between.
  • thermal shock stability is usually achieved by retaining a certain porosity, but the existence of pores will lead to a decrease in permeability resistance.
  • Corrosion resistance is achieved through high purification of raw materials and high corrosion resistance, but this brings the difficulty of sintering and how to solve the problem of permeability resistance.
  • Permeation resistance is mainly improved by improving the sintering and compactness of refractory materials.
  • the densification is achieved through the sintering process, and sintering is usually achieved through the liquid phase.
  • the refractory material is an aggregate of large particles and fine powder, the densification between particles requires a large force, and the surface tension and solid solution driving force of the liquid phase are very limited. Therefore, it is possible to change the local morphology, but cannot change the overall structure, nor can it effectively prevent the penetration of slag, unless there is a large amount of liquid phase, which is not feasible for high temperature and harsh conditions such as molten steel refining; in addition, the existence of more liquid phase also leads to The thermal shock stability of the material is greatly reduced. Therefore, the contradiction between thermal shock stability, permeability resistance and erosion resistance has not been resolved.
  • the structural formula of calcium hexaaluminate is CaO ⁇ 6Al 2 O 3 (CA6 for short), the melting point is 1875°C, and the theoretical density is 3.79g/cm 3 ; the characteristics of this material are: (1) Stability under low oxygen partial pressure Good; (2) Calcium hexaaluminate has a lamellar stacked structure, and the crystal growth is anisotropic, and the growth rate in the C-axis is slow, so it is difficult to sinter; (3) CA6 reacts with slag to generate CA2 ( CaO 2Al 2 O 3 for short), CA (CaO 2 Al 2 O 3 for short), etc., at the steelmaking temperature, CA2 is solid and CA is liquid phase, and the solid-liquid mixed phase blocks the pores and inhibits the penetration of slag .
  • the performance of inhibiting slag penetration is very suitable for refractory materials in contact with the melt, but the lamellar structure and anisotropic growth of the material cause poor sinterability and difficult densification, so it is difficult to prepare bulk density Raw materials greater than 3.0g/cm 3 and calcium hexaaluminate refractories with a bulk density greater than 2.90g/cm 3 . Without densified CA6 raw materials, it is impossible to have high-density CA6 refractories.
  • Another example is "a preparation method of dense calcium hexaaluminate refractory clinker” (CN110171980A), “a dense calcium hexaaluminate refractory clinker and its preparation method” (CN105585314A), using TiO 2 and MnO as sintering agents respectively , but this method cannot achieve densification by controlling the stacking of atoms in the mirror layer, but only uses the liquid phase to shorten the distance between the grains, but this densification is limited.
  • the method of adding sintering aids to increase the density is at the expense of the high-temperature performance of the material, which will greatly reduce the high-temperature performance of the material (although the addition is less than 1%, it will produce several times the liquid phase at high temperatures. quantity).
  • the refractory material In addition to the defects of the raw material of calcium hexaaluminate with the addition of sintering aids, the refractory material also has a high apparent porosity (the apparent porosity of the material is up to 35%) and poor corrosion resistance. question. The damage rate of calcium hexaaluminate refractories will be very fast when the porosity is high and the addition of sintering aids is high.
  • CaO ⁇ 2MgO ⁇ 8Al 2 O 3 and 2CaO ⁇ 2MgO ⁇ 14Al 2 O 3 are based on the stacking of CA6 structural units and MgO ⁇ Al 2 O 3 in the C-axis, their properties are similar to CA6.
  • CA6 is used to summarize below, and CaO ⁇ 2MgO ⁇ 8Al 2 O 3 and 2CaO ⁇ 2MgO ⁇ 14Al 2 O 3 are collectively abbreviated as CMA.
  • CMA CaO ⁇ 2MgO ⁇ 8Al 2 O 3 and 2CaO ⁇ 2MgO ⁇ 14Al 2 O 3
  • CA6 and CMA are collectively referred to as calcium hexaaluminate phases.
  • the existing problems and defects of the prior art are: (1) In order to balance the thermal shock stability and slag penetration resistance, the refractory material must retain a relatively high porosity, which will cause the slag to refractory The penetration in the material is deep, the metamorphic layer is thick, and then corrosion and peeling damage occur; (2) In order to ensure the corrosion resistance, most of the raw materials are of high purity, but it is difficult to sinter, and in order to realize the sintering and densification of the green body, it must be It is necessary to introduce sintering aids to lower the melting point and increase the liquid phase, which reduces the slag erosion resistance of the material; (3) the addition of sintering aids to promote sintering and densification only changes the local microstructure, not the overall structure.
  • the difficulty in solving the above problems and defects is as follows: (1) The existing development concept of refractory materials determines that whether it is castable or refractory bricks, the distribution of pores is uneven; in order to alleviate the stress damage caused by temperature changes, there must be A large amount of porosity is used to counteract the uneven distribution of punching pores, which makes slag penetration inevitable and difficult to control; (2) In order to enhance the resistance to slag erosion, only the purity of raw materials can be improved, and high-purity raw materials only rely on particles Diffusion is difficult to achieve sintering, and the strength cannot be guaranteed; (3) The high-purity refractory system can only achieve sintering and obtain strength in the liquid phase by adding sintering aids, but the appearance of the low-melting liquid phase leads to corrosion resistance (4) CA6 material is difficult to sinter due to its own structural characteristics.
  • the present invention provides a refractory material with high corrosion resistance, its preparation method and its application.
  • the high-corrosion-resistant refractory material described in the present invention does not need to add any sintering aids in the preparation process, and can be prepared by using a hot-pressing sintering process with high purity, good corrosion resistance, resistance to slag penetration and high thermal shock Stable refractory products.
  • a corrosion-resistant refractory material includes corundum and one or more phases selected from CA6, C2M2A14, CM2A8 and ZrO 2 .
  • corundum and one or more of them are selected from CA6, C2M2A14 , CM2A8 and ZrO The sum of phases ⁇ 90%;
  • the corundum phase is 26.5-89.5%, preferably 32-89.5%, more preferably 32.0-88.0%;
  • the sum of the total amount of CA6+C2M2A14+CM2A8 phases is 5.25-66.5%, preferably 5.25-62.0%, more preferably 6.0-62.0%;
  • the ZrO2 phase is 0-35%, preferably 0-30%.
  • the chemical composition of the refractory material includes Al 2 O 3 , CaO, MgO and ZrO 2 , in the mass of the refractory material
  • the Al 2 O 3 is 59.5-98.99%, preferably 64.57-98.99%
  • the CaO is 0.30-5.58%, preferably 0.35-5.58%, more preferably 0.30-5.20% or 0.35-5.20%
  • the MgO is 0-5.58% and the ZrO 2 is 0-35%.
  • the granular material and the fine powder are mixed to obtain a mixed material, and the mixed material is obtained by hot pressing and sintering.
  • the granules include corundum granules and mixed granules, preferably, in terms of the mass percentage in the granules, the corundum granules are 65 -100%, the mixed granular material is 0-35%;
  • the mixed granular material is selected from one or more of CA6 granular material, C2M2A14 granular material and CM2A8 granular material;
  • the corundum granules are selected from one or more of platy corundum granules, sintered corundum granules, white corundum granules, dense corundum granules and sub-white fused alumina granules.
  • the fine powder includes Al 2 O 3 -CaO-MgO fine powder and fine powder containing ZrO 2 , preferably, in fine powder
  • the mass percentage of the Al 2 O 3 -CaO-MgO series fine powder is 50-100%, and the fine powder containing ZrO 2 is 0-50%;
  • the Al 2 O 3 -CaO-MgO series fine powder includes Al 2 O 3 fine powder and one or more fine powders selected from CA6, C2M2A14, CM2A8 and MgO-CaO series fine powder pink;
  • the MgO-CaO series fine powder is a fine powder containing MgO and/or a fine powder containing CaO;
  • the fine powder containing Al 2 O 3 is selected from active ⁇ -Al 2 O 3 powder, ⁇ -Al 2 O 3 powder, ⁇ -Al 2 O 3 powder, aluminum hydroxide, industrial alumina, white corundum One or more fine powders of sintered corundum powder, sintered corundum powder and platy corundum powder;
  • the MgO-containing fine powder is selected from one or more fine powders of magnesium carbonate, light-burned magnesia, brucite, magnesium hydroxide, magnesium chloride, high-purity magnesia and fused magnesia ;
  • the CaO-containing fine powder is selected from one or more of quicklime, limestone, calcium hydroxide, CaO ⁇ Al 2 O 3 , CaO ⁇ 2Al 2 O 3 , 12CaO ⁇ 7Al 2 O 3 , CA6, C2M2A14 and CM2A8 two or more;
  • the ZrO2 - containing fine powder is selected from one or more of monoclinic zirconia, tetragonal zirconia, desiliconized zirconia and fused zirconia.
  • thermoforming is to put the mixture into a mold of a high-temperature device for hot-press sintering or to mold the mixture at normal temperature and then Putting it into a mold of a high-temperature device for hot-press sintering or performing hot-press sintering after the mixture is shaped at normal temperature and pre-sintered at low temperature.
  • a method for preparing a refractory material comprising the steps of:
  • the granular material and the fine powder are mixed to obtain a mixed material, and the mixed material is obtained by hot pressing and sintering.
  • the granules include corundum granules and mixed granules, preferably, in terms of mass percentage in the granules, the corundum granules are 65 -100%, the mixed granular material is 0-35%;
  • the mixed pellets are one or more of CA6 pellets, C2M2A14 pellets and CM2A8 pellets;
  • the corundum granules are selected from one or more of tabular corundum, sintered corundum, white corundum, dense corundum and sub-white corundum.
  • the fine powder includes Al 2 O 3 -CaO-MgO fine powder and fine powder containing ZrO 2 , preferably, in fine powder
  • the mass percentage of the Al 2 O 3 -CaO-MgO series fine powder is 50-100%, and the fine powder containing ZrO 2 is 0-50%;
  • the Al 2 O 3 -CaO-MgO series fine powder includes Al 2 O 3 fine powder and one or more fine powders selected from CA6, C2M2A14, CM2A8 and MgO-CaO series fine powder pink;
  • the MgO-CaO series fine powder is a fine powder containing MgO and/or a fine powder containing CaO;
  • the fine powder containing Al 2 O 3 is selected from active ⁇ -Al 2 O 3 powder, ⁇ -Al 2 O 3 powder, ⁇ -Al 2 O 3 powder, aluminum hydroxide, industrial alumina, white corundum One or more fine powders of sintered corundum powder, sintered corundum powder and platy corundum powder;
  • the MgO-containing fine powder is selected from one or more fine powders of magnesium carbonate, light-burned magnesia, brucite, magnesium hydroxide, magnesium chloride, sintered magnesia and fused magnesia;
  • the CaO-containing fine powder is selected from one or more of quicklime, limestone, calcium hydroxide, CaO ⁇ Al 2 O 3 , CaO ⁇ 2Al 2 O 3 , 12CaO ⁇ 7Al 2 O 3 , CA6, C2M2A14 and CM2A8 two or more;
  • the ZrO2 - containing fine powder is selected from one or more of monoclinic zirconia, tetragonal zirconia, desiliconized zirconia and fused zirconia.
  • the hot-press sintering is to put the mixture into a mold of a high-temperature device for hot-press sintering or to mold the mixture at normal temperature and then Putting it into a mold of a high-temperature device for hot-pressing sintering, or putting the mixture into a mold of a high-temperature device for hot-pressing sintering after molding at normal temperature and pre-sintering at a low temperature.
  • a working lining of a ladle for molten steel smelting comprising the refractory material described in any one of items 1-12 or the refractory material prepared by the preparation method described in any one of items 13-19.
  • a working lining for molten aluminum smelting and transporting ladles comprising the refractory material described in any one of items 1-12 or the refractory material prepared by the preparation method described in any one of items 13-19.
  • a refractory lining for an industrial furnace comprising the refractory material described in any one of items 1-12 or the refractory material prepared by the preparation method described in any one of items 13-19.
  • the refractory material described in the present invention does not use any sintering-promoting components in the preparation process, and does not realize sintering by means of liquid phase, but by means of high temperature and high pressure to promote particle rearrangement and particle diffusion. Therefore, the present invention provides Refractory materials have good high temperature performance, relatively uniform structure, and good thermal shock stability;
  • the total content of sintering-promoting components such as SiO 2 , TiO 2 , Fe 2 O 3 , R 2 O (the general name of K 2 O and Na 2 O) introduced by raw materials is ⁇ 1.5%
  • the chemical composition of the material system has high purity, which is higher than the purity of refractory materials containing calcium hexaaluminate series phases prepared by the current prior art, and can give full play to the performance advantages of high-purity raw materials, and the slag erosion resistance is very prominent;
  • the phase of the refractory material provided by the present invention includes corundum and one or two or more selected from CA6, C2M2A14, CM2A8 and ZrO2, in terms of the mass percentage of the phase of the refractory material, The sum of the total phases is ⁇ 90%, the phase purity is high, and the CA6 series phase components will generate solid-liquid components containing CA2, CA, etc. when reacting with slag, which will block the pores and enhance the material's resistance to slag erosion performance;
  • the bulk density of the refractory material provided by the present invention is 2.90-3.65g/cm 3 , which is much higher than that of the refractory material containing calcium hexaaluminate series phase prepared in the prior art; while maintaining the high purity of the material system , the high bulk density material of the present invention has greatly enhanced mechanical erosion resistance of molten steel and slag, improved slag penetration resistance, and greatly improved service life;
  • the structure of the refractory material provided by the present invention is uniform, there is no concentration of large pores, and there will be no local advanced damage.
  • the material will be corroded in a balanced and slow manner during use, and will not peel off Type of layered drop and large damage, so the service life will be greatly increased;
  • the selected raw materials are simple, and without using any sintering-promoting components, by means of a hot-pressing sintering process, the high-purity refractory material containing calcium hexaaluminate phase can be realized. Good sintering, scientific and reasonable method;
  • the corrosion-resistant refractory materials provided by the present invention can be widely used in steelmaking production lines, such as the working lining of refining ladles outside the furnace, etc., with good corrosion resistance, which greatly reduces the damage of refractory materials in the high-end special steel smelting process And the impact on molten steel improves the overall quality of high-end special steel in my country's metallurgical industry, which can increase the operating cycle of equipment, improve economic benefits, and have significant social benefits;
  • the corrosion-resistant refractory material of the present invention can also be widely used in the refractory lining of the rotary kiln, such as the transition zone of the cement rotary kiln, etc., and has good corrosion resistance and low thermal conductivity, and its performance is obviously better than that of the existing silicon molybdenum.
  • Bricks, magnesia-alumina spinel bricks and many other refractory materials can increase the operating cycle of equipment, reduce heat loss and improve economic benefits;
  • the corrosion-resistant refractory material of the present invention has very low sensitivity to the atmosphere, and can also be widely used in the masonry of industrial kilns under conditions such as high temperature, reducing atmosphere and alkaline atmosphere erosion, such as petrochemical cracking furnaces etc., with good stability, low thermal conductivity, good corrosion resistance, performance is significantly better than many refractory materials such as corundum bricks, which can increase the operating cycle of equipment, reduce heat loss, and improve economic benefits.
  • Fig. 1A is a schematic diagram showing the effect of the castable obtained in Comparative Example 1 after being eroded by dynamic rotating slag.
  • FIG. 1B is a schematic diagram of the sample effect of the refractory material described in Example 1 after being eroded by dynamic rotating slag.
  • 2A is a schematic diagram of the static crucible method for molten steel smelting in Experimental Example 2, where 1 is slag, 2 is alumina crucible, 3 is steel, 4 is aluminum, and 5 is refractory crucible.
  • Fig. 2B is the effect diagram of the corrosion of the castable obtained in Comparative Example 1 and the refractory material described in Example 1 after molten steel smelting by the static crucible method.
  • the profile structure of the obtained castable at 30 min, 40 min and 50 min, and d, e and f are the profile structures of the refractory material obtained in Example 1 at 30 min, 40 min and 50 min, respectively.
  • FIG. 2C is a schematic diagram of the comparison effect of the microstructure of the castable obtained in Comparative Example 1 and the refractory material described in Example 1.
  • FIG. 2C is a schematic diagram of the comparison effect of the microstructure of the castable obtained in Comparative Example 1 and the refractory material described in Example 1.
  • the invention provides a corrosion-resistant refractory material, the phase of the refractory material includes corundum and one or more phases selected from CA6, C2M2A14 , CM2A8 and ZrO2.
  • the phase of the refractory material is determined by XRD, for example, the measured material is ground to below 325 mesh, and then scanned by an X-ray diffractometer. By analyzing the diffraction data and matching with the standard PDF card, the relevant phase is obtained, and then the content of the relevant phase is obtained by fitting the diffraction data.
  • ZrO 2 -CaO solid solution ZrO 2 -MgO solid solution, CaO ⁇ ZrO 2 , MgO ⁇ ZrO 2 , etc. may appear in the final product phase.
  • ZrO 2 -CaO solid solution ZrO 2 -MgO solid solution, CaO ⁇ ZrO 2 , MgO ⁇ ZrO 2 and other phases, firstly combine the XRF results to correct the ZrO 2 content, and then convert the ZrO 2 content into zirconia Phase, convert CaO, MgO, etc.
  • the corundum phase is 26.5-89.5%, preferably 32-89.5%, more preferably 32.0-88.0%;
  • the sum of the total amount of CA6+C2M2A14+CM2A8 phases is 5.25-66.5%, preferably 5.25-62.0%, more preferably 6.0-62.0%;
  • the ZrO2 phase is 0-35%, preferably 0-30%.
  • the sum of the total phases can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% %, 99%, 100%, etc.
  • the corundum phase is 26.5%, 32%, 34.75%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88% , 89.5%, etc.;
  • the sum of the total amount of CA6+C2M2A14+CM2A8 phases can be 5.25%, 6%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% %, 65%, 66.5%, etc.;
  • the ZrO 2 phase can be 0, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, etc.
  • the sum of the total amount of CA6+C2M2A14+CM2A8 phase refers to the content of CA6 when only CA6 exists in the phase, and refers to the content of C2M2A14 or CM2A8 when only C2M2A14 or CM2A8 phase exists.
  • Phase content refers to the content of CA6 when only CA6 exists in the phase, and refers to the content of C2M2A14 or CM2A8 when only C2M2A14 or CM2A8 phase exists.
  • CA6 and C2M2A14 exist in the phase, it refers to the sum of the two contents; when C2M2A14 and CM2A8 exist in the phase, it refers to the sum of the contents of the two phases; when CA6 and CM2A8 exist in the phase, Refers to the sum of the contents of the two phases;
  • C2M2A14 and CM2A8 phases in the phase refers to the sum of the contents of the three phases.
  • the content of impurity components promoting sintering is ⁇ 1.5%, preferably ⁇ 1.0%.
  • the content of the sintering-promoting impurity components is 1.5%, 1.4%, 1.3%, 1.2%, 1.1%, 1.0%, 0.9%, 0.8% , 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, 0 or any range therebetween.
  • the sintering-promoting impurity components are SiO 2 , TiO 2 , Fe 2 O 3 , R 2 O, wherein R 2 O refers to alkali metal oxides, and the sintering-promoting impurity components refer to chemical Element.
  • the chemical composition of the refractory material includes Al 2 O 3 , CaO, MgO and ZrO 2 , in terms of mass percentage in the refractory material, the Al2O3 is 59.5-98.99 %, preferably 64.57-98.99%; the CaO is 0.30-5.58%, preferably 0.35-5.58%, more preferably 0.30-5.20% or 0.35-5.20%; the MgO is 0-5.58 % and the ZrO2 is 0-35%.
  • the Al 2 O 3 may be 59.5%, 61.45%, 65%, 70%, 75%, 80%, 85%, 90%, 95% in terms of mass percentage in the refractory material , 98.5%, 98.99% or any range therebetween;
  • the CaO can be 0.30%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.58% or any range therebetween;
  • the MgO can be 0, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.58% or any range therebetween;
  • the ZrO 2 may be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35% or any range therebetween.
  • the chemical composition of the refractory material is analyzed by fluorescence, that is, XRF, that is, determined according to GB/T21114-2007.
  • the bulk density of the refractory material is 2.90-3.65g/cm 3 , preferably 2.95-3.45g/cm 3 , more preferably 2.95-3.30g/cm 3 .
  • the bulk density of the refractory material can be 2.90g/cm 3 , 2.91g/cm 3 , 2.92g/cm 3 , 2.93g/cm 3 , 2.94g/cm 3 , 2.95g/cm 3 , 2.96g/cm 3 , 2.96g/cm 3 cm 3 , 2.97g/cm 3 , 2.98g/cm 3 , 2.99g/cm 3 , 3.00g/cm 3 , 3.05g/cm 3 , 3.10g/cm 3 , 3.15g/cm 3 , 3.20g/cm 3 , 3.25g/cm 3 , 3.30g/cm 3 , 3.35g/cm 3 , 3.40g/cm 3 , 3.45g/cm 3 , 3.50g/cm 3 , 3.55g/cm 3 , 3.60g/cm 3 , 3.65 g/cm 3 or any range in between.
  • the bulk density of the refractory material is measured according to GB/T2997-2000.
  • the refractory material is prepared by a method comprising the following steps:
  • the granular material and the fine powder are mixed to obtain a mixed material, and the mixed material is obtained by hot pressing and sintering.
  • the granular material refers to the part that cannot be sieved through the 180 mesh square hole sieve (Xinxiang Zhongtuo Machinery Equipment Co., Ltd.), that is, the part on the 180 mesh square hole sieve, and the particle size of the granular material is 180 mesh -10mm, that is, the particle size is 0.088-10mm, preferably 0.088-8mm, for example, the particle size of the granular material can be 0.088mm, 0.090mm, 0.095mm, 0.10mm, 0.15mm, 0.20mm, 0.25mm, 0.30mm, 0.35mm, 0.40mm, 0.45mm, 0.50mm, 0.55mm, 0.60mm, 0.65mm, 0.70mm, 0.75mm, 0.80mm, 0.85mm, 0.90mm, 0.95mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm , 7mm, 8mm, 9mm, 10mm or any range between them.
  • Described fine powder refers to the part by 180 mesh square hole sieves, promptly is positioned at the part under the sieve of 180 mesh square hole sieves, and its particle diameter ⁇ 180 mesh, namely particle diameter ⁇ 0.088mm.
  • the hot press sintering refers to a way of realizing material sintering and preparation under the joint action of applied pressure and temperature.
  • the mass ratio of the granular material to the fine powder is 30-65:35-70.
  • the mass ratio of the granular material to the fine powder is 30/70, 31/69, 32/68, 33/67, 34/66, 35/65 , 36/64, 37/63, 38/62, 39/61, 40/60, 41/59, 42/58, 43/57, 44/56, 45/55, 46/54, 47/53, 48 /52, 49/51, 50/50, 51/49, 52/48, 53/47, 54/46, 55/45, 56/44, 57/43, 58/42, 59/41, 60/40 , 61/39, 62/38, 63/37, 64/36, 65/35 or any range in between.
  • the granules include corundum granules and mixed granules, preferably, in terms of mass percentage in the granules, the corundum granules are 65- 100%, the mixed granular material is 0-35%;
  • the mixed granular material is selected from one or more of CA6 granular material, C2M2A14 granular material and CM2A8 granular material;
  • the corundum granules are selected from one or more of platy corundum granules, sintered corundum granules, white corundum granules, dense corundum granules and sub-white fused alumina granules.
  • the corundum granular material can be, for example, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% or any range therebetween ;
  • the mixed granular material can be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35% or any range therebetween.
  • the C2M2A14 granular material refers to 2CaO ⁇ 2MgO ⁇ 14Al 2 O 3 granular material
  • the CM2A8 granular material refers to CaO ⁇ 2MgO ⁇ 8Al 2 O 3 granular material.
  • the plate-shaped corundum granular material has a coarse and well-developed ⁇ -Al 2 O 3 crystal structure, an Al 2 O 3 content of more than 97.0%, a plate-shaped crystal structure, small pores and many closed pores.
  • the sintered corundum granular material refers to a refractory clinker made of industrial alumina as a raw material, which is ground into balls or blanks and sintered at a high temperature of 1750-1900 ° C. It has a large volume density, low porosity, It has excellent thermal shock resistance and slag erosion resistance at high temperature.
  • the white corundum granular material is an alumina raw material with a content of more than 97.5% of aluminum oxide (Al 2 O 3 ) prepared by electric melting of industrial alumina as a raw material, and contains a small amount of iron oxide, silicon oxide and other components. It is white.
  • the sub-white corundum granular material is produced from bauxite, and because its chemical composition and physical properties are close to those of white corundum, it is called sub-white corundum.
  • the product has the hardness of white corundum and the toughness of brown corundum. It is an ideal high-grade refractory material and abrasive material.
  • the fine powder includes Al 2 O 3 -CaO-MgO fine powder and fine powder containing ZrO 2
  • the mass of the fine powder is In terms of percentage, the Al 2 O 3 -CaO-MgO series fine powder is 50-100%, and the ZrO 2 -containing fine powder is 0-50%;
  • the Al 2 O 3 -CaO-MgO series fine powder includes Al 2 O 3 fine powder and one or more fine powders selected from CA6, C2M2A14, CM2A8 and MgO-CaO series fine powder pink;
  • the MgO-CaO series fine powder is a fine powder containing MgO and/or a fine powder containing CaO;
  • the fine powder containing Al 2 O 3 is selected from active ⁇ -Al 2 O 3 powder, ⁇ -Al 2 O 3 powder, ⁇ -Al 2 O 3 powder, aluminum hydroxide, industrial alumina, white corundum One or more of sintered corundum powder, sintered corundum powder and tabular corundum powder;
  • the MgO-containing fine powder is selected from one or more of magnesium carbonate, light-burned magnesia, brucite, magnesium hydroxide, magnesium chloride, high-purity magnesia and fused magnesia;
  • the CaO-containing fine powder is selected from quicklime, limestone, calcium hydroxide, CaO ⁇ Al 2 O 3 , CaO ⁇ 2Al 2 O 3 (CA2), 12CaO ⁇ 7Al 2 O 3 (C12A7), CA6, C2M2A14 and one or more of CM2A8;
  • the ZrO2 - containing fine powder is selected from one or more of monoclinic zirconia, tetragonal zirconia, desiliconized zirconia and fused zirconia.
  • the corundum phase can be composed of Al 2 O 3
  • CA6 can be formed from CA6 fine powder in CaO-containing raw materials and/or fine powder containing Al 2 O 3 with quicklime, limestone, calcium hydroxide, CaO ⁇ Al 2 O 3 , CaO ⁇ 2Al 2 O 3.
  • C2M2A14 can be obtained by reacting C2M2A14 fine powder and/or containing Al 2 O 3 fine powder, MgO fine powder, and CaO fine powder (except C2M2A14).
  • CM2A8 can be obtained by reacting CM2A8 fine powder and/or fine powder containing Al 2 O 3 , fine powder containing MgO, and fine powder containing CaO (except CM2A8).
  • the Al 2 O 3 -CaO-MgO series fine powder can be, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% %, 90%, 95%, 100% or any range therebetween;
  • the fine powder containing ZrO2 can be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or any range therebetween.
  • the fine powder containing Al 2 O 3 refers to the fine powder whose main chemical composition is Al 2 O 3 , or Al(OH) 3
  • the fine powder containing MgO refers to the fine powder whose chemical composition is mainly MgO or Mg(OH) 2 .
  • the fine powder containing CaO refers to the fine powder including CaO component in its chemical composition, or the fine powder including CaO, Al 2 O 3 , or the fine powder including CaO, MgO, Al 2 O 3 .
  • the fine powder containing ZrO 2 refers to a fine powder whose chemical composition is mainly ZrO 2 .
  • Active ⁇ -Al 2 O 3 powder is an alumina powder with ⁇ -Al 2 O 3 as the main ingredient and high activity obtained from industrial alumina or aluminum hydroxide as raw material and treated at 1250-1450°C;
  • ⁇ -Al 2 O 3 powder is aluminum oxide powder with high specific surface area and good adsorptive property obtained by treating aluminum hydroxide as raw material.
  • ⁇ -Al 2 O 3 powder is an alumina powder with certain hydration binding properties obtained from aluminum hydroxide as raw material through rapid high-temperature treatment at 600-900°C.
  • Industrial alumina is a mineral whose main component is ⁇ -Al 2 O 3 , which is prepared by calcining aluminum hydroxide at 900-1250°C.
  • White corundum powder is an alumina raw material with a content of more than 97.5% of aluminum oxide (Al 2 O 3 ) prepared by electric melting of industrial alumina as raw material, and contains a small amount of iron oxide, silicon oxide and other components, and is white.
  • Al 2 O 3 aluminum oxide
  • Sintered corundum powder refers to the refractory clinker made of alumina as raw material, which is ground into balls or blanks and sintered at a high temperature of 1750-1900 °C. Good thermal shock resistance and slag erosion resistance.
  • Tabular corundum powder has a coarse and well-developed ⁇ -Al 2 O 3 crystal structure, with an Al 2 O 3 content of more than 97.0%, a plate-like crystal structure, small pores and many closed pores.
  • Light-burned magnesia is a magnesium oxide-based raw material with high activity and a phase of periclase, which is prepared from magnesite (mainly composed of magnesium carbonate) and calcined at 800-1000°C.
  • Brucite is a raw material whose main component is Mg(OH) 2 .
  • Sintered magnesia is a dense magnesia raw material with MgO content ⁇ 94.5%, which is made of light-burned magnesia as raw material and calcined at high temperature.
  • Fused magnesia is a dense magnesia raw material with MgO content ⁇ 96.5% prepared from light-burned magnesia or magnesite by arc melting.
  • the quicklime also known as burnt lime
  • Monoclinic zirconia is a crystal form of zirconia stable at room temperature, and its crystal form is monoclinic.
  • Tetragonal zirconia is zirconia stabilized in the tetragonal phase.
  • Desiliconized zirconium is zirconia prepared by removing SiO 2 from zircon.
  • Fused zirconia is zirconia produced by arc melting zirconia powder.
  • hot press sintering is to put the mixed material into a mold of a high temperature device for hot press sintering or put the mixed material into a high temperature device after molding at normal temperature
  • Hot press sintering is carried out in a mould, or the mixture is molded at normal temperature and fired in a low temperature device, and then put into a mold of a high temperature device for hot press sintering.
  • putting the mixed material into a mold of a high-temperature device for hot-press sintering means that the mixed material is put into a mold of a high-temperature device to heat up, and when the temperature reaches the highest temperature, pressure is applied to achieve sintering.
  • the mixture is molded at normal temperature and then placed into a mold of a high-temperature device for hot-press sintering, which means that the mixture is pressed at normal temperature into a green body, dried and then hot-press sintered. Or apply pressure when the green body is heated to the highest temperature to achieve sintering, or continue heat preservation and pressure for a certain period of time to complete the hot-press sintering of the material; or put the green body into the mold of the high-temperature device and apply pressure when the temperature is raised to a certain temperature , and then gradually raise the temperature and increase the applied pressure at the same time until the temperature reaches the highest temperature and the pressure reaches the maximum value to complete the hot pressing sintering of the material, or continue to keep the heat and pressure for a certain period of time to complete the hot pressing sintering of the material; or the green body Put it into the mold of the high-temperature device, and gradually increase the pressure on the mixture while raising the temperature until the temperature reaches the highest temperature and the pressure reaches the maximum value, and
  • the high-temperature device is a high-temperature device commonly used by those skilled in the art, such as a high-temperature furnace.
  • the mixture After the mixture is molded at normal temperature and pre-sintered at low temperature, it is put into a mold of a high-temperature device for hot-press sintering, which means that the mixture is pressed at normal temperature and pre-sintered at 1350-1500°C, and then put into a mold of a high-temperature device hot-pressed sintering.
  • the hot pressing sintering operation is the same as above.
  • the hot pressing strength is 0.5-30 MPa.
  • the hot compressive strength is the value of the pressure exerted on the sample per unit area.
  • the temperature may be 1550°C, 1600°C, 1650°C, 1700°C, 1750°C, 1800°C or any range therebetween;
  • Hot compression strength can be, for example, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa , 9.5MPa, 10Mpa, 10.5Mpa, 11Mpa, 11.5Mpa, 12Mpa, 12.5Mpa, 13Mpa, 13.5Mpa, 14Mpa, 14.5Mpa, 15Mpa, 20Mpa, 25Mpa, 30Mpa or any range between them.
  • the invention provides a kind of preparation method of refractory material, it comprises the following steps:
  • the granular material and the fine powder are mixed to obtain a mixed material, and the mixed material is obtained by hot pressing and sintering.
  • the mass ratio of the granular material to the fine powder is 30-65:35-70.
  • the particle size of the fine powder is ⁇ 0.088mm; preferably, the particle size of the granular material is 0.088-10mm, preferably 0.088-8mm.
  • hot press sintering is to put the mixed material into a mold of a high temperature device for hot press sintering or put the mixed material into a high temperature device after molding at normal temperature
  • Hot press sintering is carried out in a mould, or the mixture is molded at normal temperature and fired in a low temperature device, and then put into a mold of a high temperature device for hot press sintering.
  • the refractory material obtained by the invention by means of high temperature and high pressure to promote particle rearrangement and particle diffusion has less high temperature liquid phase, uniform structure and good thermal shock stability.
  • the invention provides a working lining of a ladle for molten steel smelting, which comprises the above-mentioned refractory material or the refractory material prepared by the above-mentioned preparation method.
  • the invention provides a working lining for molten aluminum smelting and transporting ladles, which comprises the above-mentioned refractory material or the refractory material prepared by the above-mentioned preparation method.
  • the invention provides a refractory lining for an industrial kiln, which includes the above-mentioned refractory material or the refractory material prepared by the above-mentioned preparation method.
  • the present invention generally and/or specifically describes the materials and test methods used in the test.
  • % means wt%, ie mass percentage.
  • the reagents or instruments used, whose manufacturers are not indicated, are commercially available conventional reagent products, wherein, Table 1 shows the source of the raw materials used in the examples.
  • Sub-white corundum pellets Al 2 O 3 ⁇ 96.5% Luoyang Ruishi Company
  • CM2A8 pellets Al 2 O 3 ⁇ 84%, CaO ⁇ 5.0%, MgO ⁇ 8.0% Zibo Luzhong Refractories Co., Ltd.
  • the obtained refractory is analyzed by powder XRD, that is, the measured refractory is ground to below 325 mesh, and then scanned by an X-ray diffractometer (Bruker: D8ADVANCE).
  • XRD X-ray diffractometer
  • the relevant phases are obtained, and then the content of the relevant phases is obtained by fitting the diffraction data, so that the main phases are corundum, CM2A8, and zirconia.
  • the total amount of corundum, CM2A8 and zirconia is 99.1%, the corundum phase is 73.1%, the CM2A8 phase is 6.0%, and the zirconia phase is 20.0%.
  • the refractory material is subjected to XRF analysis according to the standard, and is measured according to GB/T21114-2007.
  • the refractory material includes 78.17% Al 2 O 3 , 0.43% MgO, 0.35% CaO, 20.0% ZrO 2 .
  • the refractory material of this example is measured according to GB/T2997-2000, and the bulk density is 3.30 g/cm 3 .
  • phase is mainly corundum, CA6 and zirconia, and in the mass percent accounted for in the phase of the refractory material measured, the total amount of corundum, CA6 and zirconia is 98.18%, the corundum phase is 65.1%, the CA6 phase is 23.4%, and the zirconia phase is 9.68%.
  • Example 2 The analysis was carried out in the same way as in Example 1, and the refractory material contained 87.12% Al 2 O 3 , 1.93% CaO, and 9.65% ZrO 2 in terms of the mass percentage of the refractory material.
  • phase is mainly corundum, CM2A8, zirconia, in the mass percent that accounts for in the phase of matter of the refractory material measured, the total amount of corundum, CM2A8, zirconia is 98.5%, the corundum phase is 32.0%, the CM2A8 phase is 36.5%, and the zirconia phase is 30%.
  • the refractory material includes 64.57% Al 2 O 3 , 2.94% MgO, 2.01% CaO, 30% ZrO 2 .
  • phase is mainly corundum and CA6, in the mass percentage accounted for in the phase of the refractory material measured, the total amount of corundum and CA6 is 98.6%, corundum phase It is 88.0%, and the CA6 phase is 10.6%.
  • the analysis was carried out in the same method as in Example 1, and the refractory material contained 98.99% Al 2 O 3 and 0.89% CaO in terms of mass percentage in the refractory material.
  • phase is mainly corundum, CA6, in the mass percent that accounts for in the phase of the refractory material that measures, corundum, CA6 total amount is 96.9%, corundum phase It is 74.5%, and the CA6 phase is 22.4%.
  • Example 2 The analysis was carried out in the same method as in Example 1, and the refractory material contained 96.6% Al 2 O 3 and 1.95% CaO in terms of the mass percentage of the refractory material.
  • phase is mainly corundum, CA6, in the mass percentage that accounts for in the phase of the refractory material measured, the total amount of corundum, CA6 is 98.1%, corundum phase It is 88.0%, and the CA6 phase is 10.1%.
  • the analysis was carried out in the same method as in Example 1, and the refractory material contained 98.99% Al 2 O 3 and 0.75% CaO in terms of the mass percentage of the refractory material.
  • phase is mainly corundum, C2M2A14, in the mass percentage accounted for in the phase of the refractory material measured, the total amount of corundum, C2M2A14 is 96.2%, corundum phase is 75.0%, and the C2M2A14 phase is 21.2%.
  • Example 2 Analysis was carried out in the same manner as in Example 1, and the refractory material contained 96.3% Al 2 O 3 , 1.0% MgO, and 1.20% CaO in terms of mass percentages in the refractory material.
  • phase mainly is corundum, CA6, in the mass percentage that accounts for in the phase of the refractory material measured, the total amount of corundum, CA6 is 97.1%, corundum phase It is 74.7%, and the CA6 phase is 22.4%.
  • Example 2 The analysis was carried out in the same method as in Example 1, and the refractory material contained 96.4% Al 2 O 3 and 1.91% CaO in terms of the mass percentage of the refractory material.
  • phase is mainly corundum, CM2A8, in the mass percentage accounted for in the phase of the refractory material measured, the total amount of corundum, CM2A8 is 95.42%, corundum phase It is 73.1%, and the CM2A8 phase is 22.32%.
  • Example 2 The analysis was carried out in the same way as in Example 1, and the refractory material contained 95.7% Al 2 O 3 , 1.97% MgO, and 1.02% CaO in terms of mass percentage of the refractory material.
  • phase mainly is corundum, CA6, in the mass percentage accounted for in the phase of the refractory material measured, the total amount of corundum, CA6 is 98.8%, corundum phase It is 36.8%, and the CA6 phase is 62.0%.
  • Example 2 The analysis was carried out in the same way as in Example 1, and the refractory material contained 93.7% Al 2 O 3 and 5.20% CaO in terms of the mass percentage of the refractory material.
  • phase is mainly corundum, CM2A8, zirconia, in the mass percent that accounts for in the phase of matter of the refractory material measured, the total amount of corundum, CM2A8, zirconia is 99.6%, the corundum phase is 26.5%, the CM2A8 phase is 38.1%, and the zirconia phase is 35%.
  • the refractory material includes 59.5% Al 2 O 3 , 3.01% MgO, 2.03% CaO and 35% ZrO 2 .
  • phase is mainly corundum, CM2A8 and zirconia, in the mass percentage accounted for in the phase of the refractory material measured, the total amount of corundum, CA6 and zirconia is 97.15%, the corundum phase is 75.4%, the CM2A8 phase is 5.25%, and the zirconia phase is 16.5%.
  • the refractory material includes 80.8% Al 2 O 3 , 0.30% CaO, 0.43% MgO, 16.9% ZrO 2 .
  • phase is mainly corundum, CA6, in the mass percentage that accounts for in the phase of the refractory material measured, the total amount of corundum and CA6 is 97.7%, corundum phase is 31.2%, and the CA6 phase is 66.5%.
  • Example 2 Analysis was carried out in the same method as in Example 1, and the refractory material contained 93.1% Al 2 O 3 and 5.58% CaO in terms of mass percentages in the refractory material.
  • phase is mainly corundum, CA6, in the mass percent that accounts for in the phase of the refractory material measured, the total amount of corundum and CA6 is 95.4%, corundum phase It is 75.1%, and the CA6 phase is 20.3%.
  • Example 2 Analysis was carried out in the same method as in Example 1, and the refractory material contained 96.1% Al 2 O 3 and 1.94% CaO in terms of mass percentages in the refractory material.
  • phase is mainly corundum, CM2A8, in the mass percentage accounted for in the phase of the refractory material measured, the total amount of corundum and CM2A8 is 98.8%, corundum phase is 36.8%, and the CM2A8 phase is 62%.
  • Example 2 The analysis was carried out in the same way as in Example 1, and the refractory material contained 90.1% Al 2 O 3 , 5.20% MgO, and 3.60% CaO in terms of mass percentage of the refractory material.
  • the maximum temperature is 1800° C.
  • the hot-press strength is 2 MPa, so as to obtain a corrosion-resistant refractory material.
  • phase is mainly corundum, CM2A8, in the mass percentage accounted for in the phase of the refractory material measured, the total amount of corundum, CM2A8 is 98.3%, corundum phase 31.8%, CM2A8 phase is 66.5%.
  • Example 2 The analysis was carried out in the same way as in Example 1, and the refractory material contained 89.3% Al 2 O 3 , 5.58% MgO, and 3.88% CaO in terms of mass percentage of the refractory material.
  • phase mainly is corundum, CM2A8, CA6, in the mass percentage accounted for in the phase of matter of the refractory material measured, the total amount of corundum, CM2A8 is 90.0%, corundum
  • the physical phase is 44.0%
  • the CM2A8 physical phase is 22.6%
  • the CA6 physical phase is 23.4%.
  • Example 2 The analysis was carried out in the same way as in Example 1, and the refractory material contained 90.8% Al 2 O 3 , 4.28% MgO, and 3.13% CaO in terms of mass percentage of the refractory material.
  • phase is mainly corundum, CA6, by the mass percentage that accounts for in the phase of the refractory material that measures, corundum, CA6 total amount is 99.53%, corundum phase It is 89.50%, and the CA6 phase is 10.3%.
  • Example 2 The analysis was carried out in the same way as in Example 1, and the refractory material contained 98.99% Al 2 O 3 and 0.84% CaO in terms of mass percentage of the refractory material.
  • Comparative Example 1 uses a conventional preparation method, that is, adopts the method of Example 1 in Chinese patent application CN107500747A to obtain a refractory material.
  • Example 2 The analysis was carried out in the same way as in Example 1.
  • the chemical composition of the obtained refractory material included Al 2 O 3 92.11%, CaO 7.02%.
  • the phases of the comparative example 1 are mainly CA6, corundum, CaO ⁇ Al 2 O 3 and CaO ⁇ 2Al 2 O 3 , and the phases of the refractory material account for In terms of mass percentage, the CA6 phase is 69.1%, the corundum phase is 24.2%, the CaO ⁇ Al 2 O 3 phase is 2.30%, and the CaO ⁇ 2Al 2 O 3 phase is 2.31%.
  • Example 1 In the dynamic slag erosion experiment, the refractory material obtained in Example 1 and the refractory material sample obtained in Comparative Example 1 were used for comparison.
  • the conditions of the dynamic slag erosion experiment are as follows: the deoxidation method adopts metal aluminum deoxidation, the experimental temperature is 1600 °C, the argon atmosphere, the slag system adopts CaO-Al 2 O 3 -SiO 2 system, the steel slag composition is CaO51%, Al 2 O 3 30 %, SiO 2 11%, MgO 8%, CaO/SiO 2 is 4.6.
  • Fig. 2A is a schematic diagram of the static crucible method for molten steel smelting.
  • the sample of embodiment 1 is first hot-pressed into a ⁇ 45mm sample, and then a ⁇ 30mm ⁇ 40mm pit is drilled therefrom.
  • the castable of Comparative Example 1 was also cast into a ⁇ 45mm sample, and the size of the internal pit was ⁇ 30mm ⁇ 40mm.
  • the experimental conditions are 1600°C, argon atmosphere, and metal aluminum deoxidation.
  • the slag system adopts CaO-Al 2 O 3 -SiO 2 system
  • the composition of steel slag is CaO 51%, Al 2 O 3 30%, SiO 2 11%, MgO 8%
  • CaO/SiO 2 is 4.6
  • the static slag erosion results are shown in the figure 2B, where a, b and c are the profile structures of the castable of Comparative Example 1 at 30 min, 40 min and 50 min respectively, and d, e and f are the profile structures of the samples of Example 1 at 30 min, 40 min and 50 min respectively.
  • Figure 2C is a comparison of the microstructure of the castable of Comparative Example 1 and the sample of Example 1 of this patent
  • a, b and c are the microstructures of the castable of Comparative Example 1 at 30min, 40min and 50min, respectively
  • d , e, f are the microstructures of the sample of Example 1 at 30min, 40min and 50min respectively. It can also be seen from the microstructure that the structure of the castable in Comparative Example 1 is very uneven, and the slag can penetrate deeply along the places with more holes, while the metamorphic layer in Example 1 of this patent is very thin. And very even. This also shows the excellent performance of the samples of the present invention.
  • the refractory materials obtained in Examples 1-17 and Comparative Example 1 were subjected to experiments on slag erosion and thermal shock stability, wherein, regarding the measurement of slag erosion: first, the crucible after the experiment was cut along the middle surface, and the Samples were taken from the crucible wall and observed and measured with an electron microscope to measure the slag erosion.
  • the thermal shock stability test was measured according to GB/T 30873-2014, and the results are shown in Table 3.
  • Example 1 100 ⁇ m 10
  • Example 2 130 ⁇ m 16
  • Example 3 124 ⁇ m 14
  • Example 4 155 ⁇ m 12
  • Example 5 142 ⁇ m 13
  • Example 6 134 ⁇ m 12
  • Example 7 147 ⁇ m 10
  • Example 8 160 ⁇ m 11
  • Example 9 158 ⁇ m 10
  • Example 10 154 ⁇ m 13
  • Example 11 133 ⁇ m 10
  • Example 12 117 ⁇ m 8
  • Example 13 165 ⁇ m 12
  • Example 14 170 ⁇ m 17
  • Example 15 183 ⁇ m 16
  • Example 16 138 ⁇ m 5
  • Example 17 210 ⁇ m 15
  • Example 18 128 ⁇ m 12 Comparative example 1 7.5mm 15
  • the addition of ZrO2 is beneficial, and the addition of CA6 has better thermal shock stability than the addition of corundum, C2M2A8, and CM2A8 refractories of the same quality; under the same composition, the bulk density is small, and the thermal shock Stability is relatively better.
  • refractory materials added with zirconia have good resistance to slag erosion and thermal shock stability. Expensive, therefore, for the embodiment of the present invention, its performance is the result of comprehensive comparison.

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Abstract

本发明公开了一种耐蚀损性耐火材料、制备方法及其应用。所述的耐蚀损性耐火材料，所述耐火材料的物相包括刚玉和选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上的物相。所述的耐火材料的高温液相量少、气孔结构均匀、热震稳定性能好，可广泛应用于炼钢生产线上，还可以广泛应用于回转窑的耐火衬体，抗侵蚀性能好、导热率低，性能明显优于现有硅莫砖、镁铝尖晶石砖等诸多耐火材料。

Description

耐蚀损性耐火材料、制备方法及其应用 技术领域
本发明涉及耐火材料技术领域，尤其涉及一种高耐蚀耐火材料、制备方法及其应用。
背景技术
铁水经转炉吹炼后由于存在较多的氧，钢水必须经过精炼工序，即主要是脱氧、脱硫和去除非金属夹杂等；这个过程一般需要较高的温度和较高的熔渣碱度。精炼过程中耐火材料的损毁是非常严重的，这主要缘于高温和高碱度炉渣。
温度高，导致熔渣对耐火材料熔蚀的速率很快，因此用于精炼钢包的工作衬一般都是比较好的耐火材料，原料的纯度较高、耐侵蚀性较好，像目前应用的刚玉-尖晶石浇注料、刚玉-MgO-SiO 2浇注料等的主要原料是刚玉。
精炼渣的碱度一般都较高、粘度较小，这主要是着眼于脱硫及改变夹杂物属性等，但这也导致熔渣在耐火材料中的渗透较深，而渗透就意味着耐火材料变质和蚀损。因变质层与原砖层的膨胀系数、高温性能等的差异较大，使耐火材料出现剥落损毁，这对耐火材料是非常致命的损毁方式。
耐火材料不同于陶瓷，耐火材料应用中一般都有较大的温度变化，承受着较大的热应力，因此，为避免耐火材料在使用中应力炸裂和破损，耐火材料中都需要保留一定的气孔率来缓冲膨胀的应力，像刚玉-尖晶石浇注料中就保留15～19％的气孔率；这些气孔在缓冲膨胀应力的同时也为低粘度熔渣的渗入提供了便利条件，导致了渗透和剥落损毁。对于现有的耐火材料制备技术和研究理念来讲，保留一定的气孔是必须的，其根本原因是避免耐火材料的应力损伤和保障热震稳定性能。
因此，用于钢包的耐火材料需要满足三点：耐侵蚀、抗渗透和抗热震稳定性能，而热震稳定性能和抗渗透性、耐侵蚀性又是相互矛盾的。
目前工业化应用的第一大类钢包工作衬材料为镁碳砖和铝镁碳砖，其思路是基于耐侵蚀性好的镁砂、刚玉等，通过添加石墨制备而成的。由于石墨 的低润湿性，阻止熔渣和钢水向耐火材料中渗透，同时，基于石墨的高导热性，降低耐火材料内部的温度梯度，改善因温度骤变导致的热应力，提高耐火材料的热震稳定性能。但石墨类材料在使用中存在向钢中增碳问题，尤其在冶炼超低碳钢时更明显，另外，石墨的氧化也导致该类材料损毁加快，因为石墨氧化即相当于增加了气孔。精炼钢包耐火材料无碳化是很重要的发展方向。
刚玉-尖晶石或刚玉-MgO-SiO 2体系浇注料是目前工业化应用的无碳耐火材料，骨料为板状刚玉、尖晶石颗粒，细粉为板状刚玉、尖晶石、活性氧化铝微粉及纯铝酸盐水泥等，该类浇注料的原料都是高纯度、高耐蚀性原料，但集合在一起构建的耐火材料却存在热震稳定性能和抗渗透性、耐侵蚀性之间的矛盾。
对无碳耐火材料，热震稳定性能的改善通常是通过保留一定的气孔率来实现的，但气孔的存在将导致抗渗透性降低。抗侵蚀性通过原料高纯化、高耐蚀化来实现，但这又带来了难以烧结的难题和如何解决抗渗透性问题。抗渗透性则主要通过提升耐火材料的烧结性和致密性来改善。为实现致密性，除通过调整颗粒级配外，就是借助烧结过程实现致密化，而烧结通常要借助液相来实现。
由于耐火材料为大颗粒和细粉的集合体，颗粒间的致密化需要较大的作用力，而液相的表面张力和固溶驱动力是很有限的，因此，借助液相烧结可能改变局部形貌，却改变不了整体结构，也无法有效阻止熔渣渗透，除非有大量液相存在，而这对于钢水精炼这样的高温和苛刻条件是不可行的；另外，较多液相的存在也导致材料的热震稳定性能大幅度下降，因此，热震稳定性能和抗渗透性、耐侵蚀性间的矛盾一直未能解决。
六铝酸钙的结构式为CaO·6Al 2O 3(简写CA6)，熔点为1875℃，理论密度为3.79g/cm 3；该材料的特点是：(1)在低氧分压下的稳定性好；(2)六铝酸钙为片层状堆叠结构，晶体生长各向异性，在C轴向的生长速率较慢，很难烧结；(3)CA6在与熔渣反应时，生成CA2(CaO·2Al 2O 3的简写)、CA(CaO·Al 2O 3的简写)等，在炼钢温度下CA2为固态、CA为液相，则固液混合相封堵气孔，抑制熔渣渗透。
抑制熔渣渗透的性能很适合用在与熔体接触部位的耐火材料，但是片层状结构和各向生长异性造成该材料的烧结性很差、致密化困难，也因此很难 制备出体积密度大于3.0g/cm 3以上的原料和体积密度大于2.90g/cm 3以上的六铝酸钙质耐火材料。没有致密化的CA6原料，就不可能有高体密的CA6质耐火材料。
目前，为实现六铝酸钙原料的致密化，大都采用添加SiO 2、TiO 2等外加剂，进而在高温下出现液相，促进其致密化烧结的。如陈肇友、柴俊兰，六铝酸钙材料及其在铝工业炉中的应用(陈肇友等，六铝酸钙材料及其在铝工业炉中的应用[J].耐火材料，2011，45(2)：122～125.)谈到博耐特(六铝酸钙的商品名)的理化性能，其中化学成分SiO 2为0.9％。又如“一种致密六铝酸钙耐火熟料的制备方法”(CN110171980A)、“一种致密六铝酸钙耐火熟料及其制备方法”(CN105585314A)，分别以TiO 2、MnO作为烧结剂，但这种方法无法通过控制镜面层原子的堆叠来实现致密化，而仅仅是借助液相拉近彼此晶粒间的距离，但这种致密化是有限的。而且采用加入烧结助剂提高致密度的方法，都是以牺牲材料的高温性能为代价的，将大幅度降低材料的高温性能(尽管加入量小于1％，但是高温下却产生数倍的液相量)。
基于添加烧结助剂的六铝酸钙原料的耐火材料除具有该原料所具有的缺陷外，还存在显气孔率较高(该材料显气孔率，最高为35％)、耐侵蚀性较差等问题。六铝酸钙质耐火材料在气孔率较高、外加烧结助剂加入量较高情况下的损毁速率将是很快的。
鉴于CaO·2MgO·8Al 2O 3和2CaO·2MgO·14Al 2O 3都是基于CA6结构单元与MgO·Al 2O 3在C轴向堆叠而成，其性质类似于CA6。为便于叙述，下面仅以CA6来概括，并将CaO·2MgO·8Al 2O 3和2CaO·2MgO·14Al 2O 3统一简写为CMA。另外，将CA6和CMA统一称为六铝酸钙系物相。
因此，基于六铝酸钙化学成分上优势的前提下，如何大幅度提升材料的致密度和结构均匀性，减少钢水及熔渣的渗入，减少变质层和损毁层，提高使用寿命，如何提升六铝酸钙材料的纯度、增强抗熔渣侵蚀性能，提高使用寿命，针对精炼钢包包衬耐火材料和冶炼铝液等容器耐火材料都是非常关键的。
通过上述分析，现有技术存在的问题及缺陷为：(1)为兼顾热震稳定性和抗熔渣渗透性的平衡，耐火材料必须保留较高的气孔率，由此将导致熔渣向耐火材料中渗透较深，变质层较厚，继而发生蚀损和剥落损毁；(2)为保障耐侵蚀性，原料大都采用高纯度，但很难烧结，而为实现坯体烧结和致密 化，必须要引入烧结助剂来降低熔点、增加液相，如此又降低了材料的耐熔渣侵蚀性；(3)采用添加烧结助剂来促进烧结和致密化，仅仅是改变局部微结构，整体结构不会有太大的改变，材料尽管有所致密化但结构均匀性较差；(4)目前还没有规模化生产的致密CA6耐火原料，尽管有少量致密CA6原料生产，但该原料中含有SiO 2等烧结助剂；(5)较多助烧结液相的存在将导致材料热震稳定性能大幅度下降；(6)热震稳定性能和抗渗透性、耐侵蚀性之间的矛盾仍未解决。
解决以上问题及缺陷的难度为：(1)现有的耐火材料研制理念决定了，不论是浇注料，还是耐火砖，其气孔分布是不均匀的；为了缓解温度变化导致的应力损伤，必须有较大量的气孔率来对冲气孔分布的不均匀，由此导致熔渣渗透不可避免且很难控制；(2)为增强抗熔渣侵蚀性，只能提高原料纯度，而高纯原料仅靠质点扩散是很难达到烧结的，强度也没法得到保障；(3)高纯耐火材料体系仅能通过添加烧结助剂，以液相实现烧结、获得强度，但低熔点液相的出现导致耐侵蚀降低；(4)CA6材料由于自身结构特点导致其很难烧结，添加烧结助剂尽管可以实现致密化，但高温性能降低、耐熔渣侵蚀性下降很大、抗热震稳定性下降；(5)现有的耐火材料研制理念决定了，基于颗粒最紧密堆积、借助液相的表面张力是很难达到较高致密度的。
解决以上问题及缺陷的意义为：基于高纯度、高耐蚀损性原料，在不添加任何烧结助剂、不生成低熔点液相、不依赖液相烧结的情况下，制得高纯度、耐侵蚀性的耐火材料，能够充分发挥高纯原料耐侵蚀性上的优势；构建出组织结构均匀的耐火材料，不但从整体上解决了耐火材料的结构应力，而且解决了抗熔渣渗透性能，实现了抗渗透性和抗热震稳定性能的协调统一；如此不但充分发挥高纯原料耐侵蚀性好的优势，而且兼顾了热震稳定性能和抗熔渣渗透性的矛盾，也解决了苛刻的精炼条件对钢包工作衬耐火材料的损毁过快问题，经济效益和社会经济效益非常显著。
发明内容
为了解决上述问题，本发明提供了一种高耐蚀损性耐火材料、其制备方法及其应用。
本发明所述的高耐蚀损性耐火材料，在制备过程中无需加入任何烧结助剂，采用热压烧结工艺，可制备出纯度高、耐侵蚀性好、抗熔渣渗透且具有较高热震稳定性的耐火材料制品。
本发明具体技术方案如下：
1.一种耐蚀损性耐火材料，所述耐火材料的物相包括刚玉和选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上的物相。
2.根据项1所述的耐火材料，其中，以在所述耐火材料的物相所占的质量百分比计，刚玉以及选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上的物相之和≥90％；
优选的，刚玉物相为26.5-89.5％，优选为32-89.5％，进一步优选为32.0-88.0％；
CA6+C2M2A14+CM2A8物相总量之和为5.25-66.5％，优选为5.25-62.0％，进一步优选6.0-62.0％；以及
ZrO 2物相为0-35％，优选为0-30％。
3.根据项1或2所述的耐火材料，其中，以在所述耐火材料中所占的质量百分比计，促烧结的杂质组分含量≤1.5％，优选≤1.0％。
4.根据项1-3中任一项所述的耐火材料，其中，所述耐火材料的化学成分包括Al 2O 3、CaO、MgO和ZrO 2，以在所述耐火材料中所占的质量百分比计，所述Al 2O 3为59.5-98.99％，优选为64.57-98.99％；所述CaO为0.30-5.58％，优选为0.35-5.58％，进一步优选为0.30-5.20％或0.35-5.20％；所述MgO为0-5.58％以及所述ZrO 2为0-35％。
5.根据项1-4中任一项所述的耐火材料，其中，所述耐火材料的体积密度为2.90-3.65g/cm 3，优选为2.95-3.45g/cm 3，进一步优选为2.95-3.30g/cm 3。
6.根据项1-5中任一项所述的耐火材料，其中，所述耐火材料通过包含下述步骤的方法制备得到：
将颗粒料和细粉混合得到混合料，将所述混合料进行热压烧结得到。
7.根据项6所述的耐火材料，其中，所述颗粒料与所述细粉的质量比例为30-65:35-70。
8.根据项6或7所述的耐火材料，其中，所述颗粒料包括刚玉颗粒料和混合颗粒料，优选的，以在颗粒料中所占的质量百分比计，所述刚玉颗粒料为65-100％，所述混合颗粒料为0-35％；
优选的，所述混合颗粒料选自CA6颗粒料、C2M2A14颗粒料和CM2A8颗粒料中的一种或两种以上；
优选的，所述刚玉颗粒料选自板状刚玉颗粒料、烧结刚玉颗粒料、白刚玉颗粒料、致密刚玉颗粒和亚白刚玉颗粒料中的一种或两种以上。
9.根据项6-8中任一项所述的耐火材料，其中，所述细粉包括Al 2O 3-CaO-MgO系细粉和含ZrO 2的细粉，优选的，以在细粉中所占的质量百分比计，所述Al 2O 3-CaO-MgO系细粉为50-100％，所述含ZrO 2的细粉为0-50％；
优选的，所述Al 2O 3-CaO-MgO系细粉包括含Al 2O 3的细粉以及选自CA6、C2M2A14、CM2A8和MgO-CaO系细粉中的一种或两种以上的细粉；
优选的，所述MgO-CaO系细粉为含MgO的细粉和/或含CaO的细粉；
优选的，所述含Al 2O 3的细粉选自活性α-Al 2O 3粉、γ-Al 2O 3粉、ρ-Al 2O 3粉、氢氧化铝、工业氧化铝、白刚玉粉、烧结刚玉粉和板状刚玉粉中的一种或两种以上的细粉；
优选的，所述含MgO的细粉选自碳酸镁、轻烧氧化镁、水镁石、氢氧化镁、氯化镁、高纯氧化镁和电熔氧化镁中的一种或两种以上的细粉；
优选的，所述含CaO的细粉选自生石灰、石灰石、氢氧化钙、CaO·Al 2O 3、CaO·2Al 2O 3、12CaO·7Al 2O 3、CA6、C2M2A14和CM2A8中一种或两种以上；
优选的，所述含ZrO 2的细粉选自单斜氧化锆、四方氧化锆、脱硅锆和电熔氧化锆中的一种或两种以上。
10.根据项6-9中任一项所述的耐火材料，其中，所述细粉的粒径≤0.088mm；优选的，所述颗粒料的粒径为0.088-10mm,优选为0.088-8mm。
11.根据项6-10中任一项所述的耐火材料，其中，所述热压烧结为将混合料放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型后再放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型和低温预烧结后进行热压烧结。
12.根据项11所述的耐火材料，其中，热压烧结的温度为1550-1800℃，优选的，热压强度为0.5-30MPa。
13.一种耐火材料的制备方法，其包括下述步骤：
将颗粒料和细粉混合得到混合料，将所述混合料进行热压烧结得到。
14.根据项13所述的制备方法，其中，所述颗粒料与所述细粉的质量比 例为30-65:35-70。
15.根据项13或14所述的制备方法，其中，所述颗粒料包括刚玉颗粒料和混合颗粒料，优选的，以在颗粒料中所占的质量百分比计，所述刚玉颗粒料为65-100％，所述混合颗粒料为0-35％；
优选的，所述混合颗粒料为CA6颗粒料、C2M2A14颗粒料和CM2A8颗粒料中的一种或两种以上；
优选的，所述刚玉颗粒料选自板状刚玉、烧结刚玉、白刚玉、致密刚玉和亚白刚玉中的一种或两种以上。
16.根据项13-15中任一项所述的制备方法，其中，所述细粉包括Al 2O 3-CaO-MgO系细粉和含ZrO 2的细粉，优选的，以在细粉中所占的质量百分比计，所述Al 2O 3-CaO-MgO系细粉为50-100％，所述含ZrO 2的细粉为0-50％；
优选的，所述Al 2O 3-CaO-MgO系细粉包括含Al 2O 3的细粉以及选自CA6、C2M2A14、CM2A8和MgO-CaO系细粉中的一种或两种以上的细粉；
优选的，所述MgO-CaO系细粉为含MgO的细粉和/或含CaO的细粉；
优选的，所述含Al 2O 3的细粉选自活性α-Al 2O 3粉、γ-Al 2O 3粉、ρ-Al 2O 3粉、氢氧化铝、工业氧化铝、白刚玉粉、烧结刚玉粉和板状刚玉粉中的一种或两种以上的细粉；
优选的，所述含MgO的细粉选自碳酸镁、轻烧氧化镁、水镁石、氢氧化镁、氯化镁、烧结氧化镁和电熔氧化镁中的一种或两种以上的细粉；
优选的，所述含CaO的细粉选自生石灰、石灰石、氢氧化钙、CaO·Al 2O 3、CaO·2Al 2O 3、12CaO·7Al 2O 3、CA6、C2M2A14和CM2A8中一种或两种以上；
优选的，所述含ZrO 2的细粉选自单斜氧化锆、四方氧化锆、脱硅锆和电熔氧化锆中的一种或两种以上。
17.根据项13-16中任一项所述的制备方法，其中，所述细粉的粒径≤0.088mm；优选的，所述颗粒料的粒径为0.088-10mm，优选为0.088-8mm。
18.根据项13-17中任一项所述的制备方法，其中，所述热压烧结为将混合料放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型后再放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型和低温预烧结后再放入高温装置的模具中进行热压烧结。
19.根据项18所述的制备方法，其中，所述热压烧结的温度为 1550-1800℃，优选的，热压强度为0.5-30MPa。
20.一种钢水冶炼用钢包的工作衬，其包括项1-12中任一项所述的耐火材料或者项13-19中任一项所述的制备方法制备得到的耐火材料。
21.一种铝液冶炼和输运包的工作衬，其包括项1-12中任一项所述的耐火材料或者项13-19中任一项所述的制备方法制备得到的耐火材料。
22.一种工业窑炉的耐火材料衬体，其包括项1-12中任一项所述的耐火材料或者项13-19中任一项所述的制备方法制备得到的耐火材料。
发明的效果
(1)本发明所述的耐火材料在制备过程中不使用任何促烧结组分，不是借助液相量实现烧结的，而是借助高温高压促进颗粒重排和质点扩散，因此，本发明提供的耐火材料的高温性能好、组织结构较为均匀、热震稳定性能好；
(2)本发明提供的耐火材料，由原料引入的SiO 2、TiO 2、Fe 2O 3、R 2O(K 2O和Na 2O的总称)等促烧结组分的总含量≤1.5％，材料体系的化学成分纯度高，高于目前现有技术所制备的含六铝酸钙系物相的耐火材料的纯度，能够充分发挥高纯原料的性能优势，耐熔渣侵蚀性非常突出；
(3)本发明提供的耐火材料的物相包括刚玉及选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上，以在所述耐火材料的物相所占的质量百分比计，总物相之和≥90％，物相纯度高，且CA6系物相组分在与熔渣反应时生成含有CA2、CA等的固液组分，堵塞气孔，增强材料的抗熔渣侵蚀的性能；
(4)本发明提供的耐火材料的体积密度为2.90～3.65g/cm 3，大大高于现有技术制备的含六铝酸钙系物相的耐火材料；在保持材料体系高纯度的情况下，高体密的本发明材料的耐钢水和熔渣的机械冲刷性大大增强，抗熔渣渗透性提高，使用寿命也大幅度提高；
(5)本发明提供的耐火材料的组织结构均匀、不存在大孔集中之处，也不会出现局部超前损毁问题，该材料在使用过程中将是均衡、缓慢被腐蚀掉，不会出现剥落型的层状掉落和大块损毁，因此使用寿命将大幅度增加；
(6)本发明提供的制备方法，选用的原料简单，在不使用任何促烧结组分的情况下，借助于热压烧结工艺，可以实现含六铝酸钙系物相的高纯耐 火材料的良好烧结，方法科学合理；
(7)本发明提供的耐蚀损性耐火材料可广泛应用于炼钢生产线上，如炉外精炼钢包工作衬等，抗侵蚀性能好，极大降低了高端特殊钢冶炼过程中耐火材料的损毁和对钢水的影响，提高了我国冶金行业高端特殊钢整体品质，能够增加设备运行周期，提高经济效益，社会效益显著；
(8)本发明的耐蚀损性耐火材料还可以广泛应用于回转窑的耐火衬体，如水泥回转窑的过渡带等，抗侵蚀性能好、导热率低，性能明显优于现有硅莫砖、镁铝尖晶石砖等诸多耐火材料，能够增加设备运行周期，减少热量散失，提高经济效益；
(9)本发明的耐蚀损性耐火材料对气氛的敏感性很低，还可以广泛应用于高温、还原性气氛及碱性气氛侵蚀等条件下的工业窑炉的砌筑，如石化裂解炉等，稳定性好、导热率低、抗侵蚀性能好，性能明显优于现有刚玉砖等诸多耐火材料，能够增加设备运行周期，减少热量散失，提高经济效益。
附图说明
图1A是对比例1所得到的浇注料经动态旋转渣侵蚀后的效果示意图。
图1B是实施例1所述的耐火材料经动态旋转渣侵蚀后的试样效果示意图。
图2A是实验例2中进行钢水冶炼的静态坩埚法示意图，其中，1为渣，2为氧化铝坩埚，3为钢，4为铝，5为耐火材料坩埚。
图2B是经静态坩埚法进行钢水冶炼后的对比例1所得到的浇注料和实施例1所述的耐火材料随时间不同时的侵蚀情况效果图，a、b和c分别为对比例1所得到的浇注料在30min、40min和50min的轮廓结构，而d、e和f分别为实施例1所得到的耐火材料在30min、40min和50min的轮廓结构。
图2C是对比例1所得到的浇注料和实施例1所述的耐火材料的显微结构对比效果示意图。
具体实施方式
下面结合附图所描述的实施方式对本发明做以详细说明，其中所有附图中相同的数字表示相同的特征。虽然附图中显示了本发明的具体实施例，然而应当理解，可以以各种形式实现本发明而不应被这里阐述的实施例所限制。 相反，提供这些实施例是为了能够更透彻地理解本发明，并且能够将本发明的范围完整的传达给本领域的技术人员。
需要说明的是，在说明书及权利要求当中使用了某些词汇来指称特定组件。本领域技术人员应可以理解，技术人员可能会用不同名词来称呼同一个组件。本说明书及权利要求并不以名词的差异作为区分组件的方式，而是以组件在功能上的差异作为区分的准则。如在通篇说明书及权利要求当中所提及的“包含”或“包括”为开放式用语，故应解释成“包含但不限定于”。说明书后续描述为实施本发明的较佳实施方式，然而所述描述乃以说明书的一般原则为目的，并非用以限定本发明的范围。本发明的保护范围当视所附权利要求所界定者为准。
本发明提供了一种耐蚀损性耐火材料，所述耐火材料的物相包括刚玉和选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上的物相。
所述耐火材料的物相通过XRD测定，例如将所测物料进行研磨至325目以下，然后利用X-射线衍射仪进行扫描。通过对衍射数据进行分析，并与标准PDF卡的匹配，得到相关物相，然后通过对衍射数据的拟合得到相关物相的含量。
关于ZrO 2物相，因H fO 2与ZrO 2共生，很难分离，且晶型相近，所以，
①H fO 2物相计入ZrO 2中；
②因温度、工艺等不同，以及成分分布不是很均匀(不可能做到绝对均匀)，最终产品中可能出现ZrO 2-CaO固溶体、ZrO 2-MgO固溶体、CaO·ZrO 2、MgO·ZrO 2等物相。在出现ZrO 2-CaO固溶体、ZrO 2-MgO固溶体、CaO·ZrO 2、MgO·ZrO 2等物相的情况下，首先结合XRF结果校正ZrO 2含量，再将这个ZrO 2含量折合为氧化锆物相，将被固溶或以CaO·ZrO 2、MgO·ZrO 2等形式结合的CaO、MgO等折合为CA6、CMA(首先将这个CaO、MgO含量折合为CA6、MA，再根据温度或CaO-MgO-Al 2O 3系成分等折合为CA6、CMA等)，然后将所有物相归一化为100％，计算出各物相的百分比含量。
关于ZrO 2在化学成分中的含量，因H fO 2与ZrO 2共生，很难分离，所以在本专利的XRF中，HfO 2含量被计算在ZrO 2含量中。
在本发明优选的一种具体实施方式中，其中，以在所述耐火材料的物相所占的质量百分比计，刚玉以及选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上的物相之和≥90％；
优选的，刚玉物相为26.5-89.5％，优选32-89.5％，进一步优选为32.0-88.0％；
CA6+C2M2A14+CM2A8物相总量之和为5.25-66.5％，优选为5.25-62.0％，进一步优选为6.0-62.0％；以及
ZrO 2物相为0-35％，优选为0-30％。
例如，以在所述耐火材料的物相所占的质量百分比计，总物相之和可以为90％、91％、92％、93％、94％、95％、96％、97％、98％、99％、100％等。
所述刚玉物相为26.5％、32％、34.75％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％、85％、88％、89.5％等；
CA6+C2M2A14+CM2A8物相总量之和可以为5.25％、6％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、66.5％等；
ZrO 2物相可以为0、1％、5％、10％、15％、20％、25％、30％、35％等。
其中，CA6+C2M2A14+CM2A8物相总量之和指的是当物相中仅存在CA6时，指的是CA6的含量，当仅存在C2M2A14或CM2A8物相时，分别指的是C2M2A14或CM2A8物相的含量
当物相中存在CA6和C2M2A14时指的是二者含量之和，当物相中存在C2M2A14和CM2A8时，指的是二者物相的含量之和；当物相中存在CA6和CM2A8时，指的是该二者物相的含量之和；
当物相中存在CA6、C2M2A14和CM2A8物相时，指的是三者物相的含量之和。
在本发明优选的一种具体实施方式中，其中，以在所述耐火材料中所占的质量百分比计，促烧结的杂质组分含量≤1.5％，优选≤1.0％。
例如，以在所述耐火材料中所占的质量百分比计，所述促烧结的杂质组分的含量为1.5％、1.4％、1.3％、1.2％、1.1％、1.0％、0.9％、0.8％、0.7％、0.6％、0.5％、0.4％、0.3％、0.2％、0.1％、0或其之间的任意范围。
所述促烧结的杂质组分为SiO 2、TiO 2、Fe 2O 3、R 2O，其中，R 2O指的是碱金属的氧化物，所述促烧结的杂质组分指的是化学成分。
在本发明优选的一种具体实施方式中，其中，所述耐火材料的化学成分包括Al 2O 3、CaO、MgO和ZrO 2，以在所述耐火材料中所占的质量百分比计，所述Al 2O 3为59.5-98.99％，优选为64.57-98.99％；所述CaO为0.30-5.58％，优选为0.35-5.58％，进一步优选为0.30-5.20％或0.35-5.20％；所述MgO为 0-5.58％以及所述ZrO 2为0-35％。
例如，以在所述耐火材料中所占的质量百分比计，所述Al 2O 3可以为59.5％、61.45％、65％、70％、75％、80％、85％、90％、95％、98.5％、98.99％或其之间的任意范围；
所述CaO可以为0.30％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.58％或其之间的任意范围；
所述MgO可以为0、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.58％或其之间的任意范围；
所述ZrO 2可以为0、5％、10％、15％、20％、25％、30％、35％或其之间的任意范围。
所述耐火材料的化学成分通过荧光即XRF分析，即按照GB/T21114-2007进行测定。
在本发明优选的一种具体实施方式中，其中，所述耐火材料的体积密度为2.90-3.65g/cm 3，优选为2.95-3.45g/cm 3，进一步优选为2.95-3.30g/cm 3。
例如，所述耐火材料的体积密度可以为2.90g/cm 3、2.91g/cm 3、2.92g/cm 3、2.93g/cm 3、2.94g/cm 3、2.95g/cm 3、2.96g/cm 3、2.97g/cm 3、2.98g/cm 3、2.99g/cm 3、3.00g/cm 3、3.05g/cm 3、3.10g/cm 3、3.15g/cm 3、3.20g/cm 3、3.25g/cm 3、3.30g/cm 3、3.35g/cm 3、3.40g/cm 3、3.45g/cm 3、3.50g/cm 3、3.55g/cm 3、3.60g/cm 3、3.65g/cm 3或其之间的任意范围。
所述耐火材料的体积密度按照GB/T2997-2000来测定。
在本发明优选的一种具体实施方式中，其中，所述耐火材料通过包含下述步骤的方法制备得到：
将颗粒料和细粉混合得到混合料，将所述混合料进行热压烧结得到。
所述颗粒料指的是经180目方孔筛(新乡市众拓机械设备有限公司)而无法筛下的部分，即位于180目方孔筛筛上的部分，颗粒料的粒径为180目-10mm，即粒径为0.088-10mm，优选为0.088-8mm，例如，颗粒料的粒径可以为0.088mm、0.090mm、0.095mm、0.10mm、0.15mm、0.20mm、0.25mm、0.30mm、0.35mm、0.40mm、0.45mm、0.50mm、0.55mm、0.60mm、0.65mm、0.70mm、0.75mm、0.80mm、0.85mm、0.90mm、0.95mm、1mm、2mm、3mm、4mm、5mm、6mm、7mm、8mm、9mm、10mm或其之间的任意范围。
所述细粉指的是通过180目方孔筛的部分，即位于180目方孔筛的筛下 部分，其粒径≤180目，即粒径≤0.088mm。
所述热压烧结指的是在施加压力和温度的共同作用下实现材料烧结和制备的一种方式。
在本发明优选的一种具体实施方式中，其中，所述颗粒料与所述细粉的质量比例为30-65:35-70。
例如，所述颗粒料与所述细粉的质量比例(即颗粒料/细粉的质量之比)为30/70、31/69、32/68、33/67、34/66、35/65、36/64、37/63、38/62、39/61、40/60、41/59、42/58、43/57、44/56、45/55、46/54、47/53、48/52、49/51、50/50、51/49、52/48、53/47、54/46、55/45、56/44、57/43、58/42、59/41、60/40、61/39、62/38、63/37、64/36、65/35或其之间的任意范围。
在本发明优选的一种具体实施方式中，其中，所述颗粒料包括刚玉颗粒料和混合颗粒料，优选的，以在颗粒料中所占的质量百分比计，所述刚玉颗粒料为65-100％，所述混合颗粒料为0-35％；
优选的，所述混合颗粒料选自CA6颗粒料、C2M2A14颗粒料和CM2A8颗粒料中的一种或两种以上；
优选的，所述刚玉颗粒料选自板状刚玉颗粒料、烧结刚玉颗粒料、白刚玉颗粒料、致密刚玉颗粒和亚白刚玉颗粒料中的一种或两种以上。
以在颗粒料中所占的质量百分比计，所述刚玉颗粒料例如可以为65％、70％、75％、80％、85％、90％、95％、100％或其之间的任意范围；
所述混合颗粒料可以为0、5％、10％、15％、20％、25％、30％、35％或其之间的任意范围。
所述C2M2A14颗粒料指的是2CaO·2MgO·14Al 2O 3颗粒料，CM2A8颗粒料指的是CaO·2MgO·8Al 2O 3颗粒料。
所述板状刚玉颗粒料具有结晶粗大、发育良好的α-Al 2O 3晶体结构，Al 2O 3的含量在97.0％以上，板片状晶体结构，气孔小且闭气孔较多。
所述烧结刚玉颗粒料指以工业氧化铝为原料，经磨细制成料球或坯体，在1750-1900℃的高温下烧结而成的耐火熟料，具有体积密度大、气孔率低、高温下有极好的抗热震性和抗炉渣侵蚀性。
所述白刚玉颗粒料是以工业氧化铝为原料经电熔融化制备的三氧化二铝(Al 2O 3)含量在97.5％以上的氧化铝原料，并含有少量氧化铁、氧化硅等成分，呈白色。
所述亚白刚玉颗粒料是以铝矾土为原料生产的，由于其化学成份和物理性能均与白刚玉接近，故称之为亚白刚玉。该产品具有白刚玉的硬度，同时兼有棕刚玉的韧性，是理想的高级耐火材料和研磨材料。
在本发明优选的一种具体实施方式中，其中，所述细粉包括Al 2O 3-CaO-MgO系细粉和含ZrO 2的细粉，优选的，以在细粉中所占的质量百分比计，所述Al 2O 3-CaO-MgO系细粉为50-100％，所述含ZrO 2的细粉为0-50％；
优选的，所述Al 2O 3-CaO-MgO系细粉包括含Al 2O 3的细粉以及选自CA6、C2M2A14、CM2A8和MgO-CaO系细粉中的一种或两种以上的细粉；
优选的，所述MgO-CaO系细粉为含MgO的细粉和/或含CaO的细粉；
优选的，所述含Al 2O 3的细粉选自活性α-Al 2O 3粉、γ-Al 2O 3粉、ρ-Al 2O 3粉、氢氧化铝、工业氧化铝、白刚玉粉、烧结刚玉粉和板状刚玉粉中的一种或两种以上；
优选的，所述含MgO的细粉选自碳酸镁、轻烧氧化镁、水镁石、氢氧化镁、氯化镁、高纯氧化镁和电熔氧化镁中的一种或两种以上；
优选的，所述含CaO的细粉选自生石灰、石灰石、氢氧化钙、CaO·Al 2O 3、CaO·2Al 2O 3(CA2)、12CaO·7Al 2O 3(C12A7)、CA6、C2M2A14和CM2A8中一种或两种以上；
优选的，所述含ZrO 2的细粉选自单斜氧化锆、四方氧化锆、脱硅锆和电熔氧化锆中的一种或两种以上。
鉴于Al 2O 3-CaO-MgO系细粉经高温热压烧结后的物相包含刚玉物相及CA6、CM2A8、C2M2A14中的一种或几种，所以，刚玉物相可由含Al 2O 3的细粉高温转化而来，CA6可由含CaO原料中的CA6细粉和/或含Al 2O 3的细粉与生石灰、石灰石、氢氧化钙、CaO·Al 2O 3、CaO·2Al 2O 3、12CaO·7Al 2O 3等含CaO原料反应而得到，C2M2A14可由C2M2A14细粉和/或含Al 2O 3细粉、含MgO细粉、含CaO细粉(除C2M2A14外)反应得到。CM2A8可由CM2A8细粉和/或含Al 2O 3细粉、含MgO细粉、含CaO细粉(除CM2A8外)反应得到。
以在细粉中所占的质量百分比计，所述Al 2O 3-CaO-MgO系细粉例如可以为50％、55％、60％、65％、70％、75％、80％、85％、90％、95％、100％或其之间的任意范围；
所述含ZrO 2的细粉可以为0、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％或其之间的任意范围。
所述含Al 2O 3的细粉指的是主要化学成分为Al 2O 3，或Al(OH) 3的细粉
含MgO的细粉是指化学成分主要为MgO或Mg(OH) 2的细粉。
含CaO的细粉指的是指其化学成分中包括CaO组分的细粉，或包括CaO、Al 2O 3的细粉，或包括CaO、MgO、Al 2O 3的细粉。
所述含ZrO 2的细粉指的是化学成分主要为ZrO 2的细粉。
活性α-Al 2O 3粉是以工业氧化铝、或氢氧化铝等为原料，经1250-1450℃处理而得到的以α-Al 2O 3为主、活性较高的氧化铝粉体；
γ-Al 2O 3粉是以氢氧化铝为原料经处理而得到的比表面积较高、吸附性较好的氧化铝粉体。
ρ-Al 2O 3粉是以氢氧化铝为原料经600-900℃高温快速处理而得到的具有一定水化结合性的氧化铝粉体。
工业氧化铝主要成分为α-Al 2O 3的矿物，是以氢氧化铝为原料，经900～1250℃煅烧制备而成的。
白刚玉粉是以工业氧化铝为原料经电熔融化制备的三氧化二铝(Al 2O 3)含量在97.5％以上的氧化铝原料，并含有少量氧化铁、氧化硅等成分，呈白色。
烧结刚玉粉指以氧化铝为原料，经磨细制成料球或坯体，在1750-1900℃的高温下烧结而成的耐火熟料，具有体积密度大、气孔率低、高温下有极好的抗热震性和抗炉渣侵蚀性。
板状刚玉粉具有结晶粗大、发育良好的α-Al 2O 3晶体结构，Al 2O 3的含量在97.0％以上，板片状晶体结构，气孔小且闭气孔较多而。
轻烧氧化镁是以菱镁矿(主要成分为碳酸镁)为原料，经800-1000℃煅烧而制备的活性较高、物相为方镁石的氧化镁系原料。
水镁石是以Mg(OH) 2为主要成分的原料。
烧结氧化镁是以轻烧氧化镁为原料，经高温煅烧而成、MgO含量≥94.5％的致密氧化镁原料。
电熔氧化镁是以轻烧氧化镁或菱镁矿为原料，经电弧熔融制备的MgO含量≥96.5％的致密氧化镁原料。
所述生石灰，又称烧石灰，主要成分为氧化钙，通常制法为将主要成分 为碳酸钙的天然岩石，在高温下煅烧，即可分解生成二氧化碳以及氧化钙(化学式：CaO，即生石灰，又称云石)。
单斜氧化锆是常温稳定的氧化锆晶型，其存在晶型为单斜形式。
四方氧化锆是以四方相形式稳定的氧化锆。
脱硅锆是以锆英石脱除其中的SiO 2等制备的氧化锆。
电熔氧化锆是以氧化锆粉体经电弧熔融制备的氧化锆。
在本发明优选的一种具体实施方式中，其中，所述热压烧结为将混合料放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型后再放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型和低温装置烧成后再放入高温装置的模具中进行热压烧结。
例如，对于将所述混合料放入高温装置的模具中进行热压烧结，是指将混合好的物料放入高温装置的模具中升温，待温度升至最高温度时进行施加压力，达到烧结，或持续保温保压一定时间，完成对材料的热压烧结；或将混合料放入高温装置的模具中升温至一定温度时施加压力，然后逐渐升温并同时增加施加的压力，直至温度达到最高温度，压力达到最大值，完成对材料的热压烧结，或持续保温保压一定时间，完成对材料的热压烧结；或将混合料放入高温装置的模具中，边升温边逐步提高施加在混合料上的压力，直至温度达到最高温度，压力达到最大值，完成对材料的热压烧结，或持续保温保压一定时间，完成对材料的热压烧结。
将所述混合料经常温成型后再放入高温装置的模具中进行热压烧结，是指将混合料经常温压制成坯体、烘干后再进行热压烧结。或将坯体升温至最高温度时进行施加压力，达到烧结，或持续保温保压一定时间，完成对材料的热压烧结；或将坯体放入高温装置的模具中升温至一定温度时施加压力，然后逐渐升温并同时增加施加的压力，直至温度达到最高温度，压力达到最大值，完成对材料的热压烧结，或持续保温保压一定时间，完成对材料的热压烧结；或将坯体放入高温装置的模具中，边升温边逐步提高施加在混合料上的压力，直至温度达到最高温度，压力达到最大值，完成对材料的热压烧结，或持续保温保压一定时间，完成对材料的热压烧结。
所述高温装置是本领域技术人员常用的高温装置，例如高温炉。
将所述混合料经常温成型和低温预烧结后再放入高温装置的模具中进行热压烧结，是指将混合料经常温压制成型和1350-1500℃预烧结后再放入 高温装置的模具中进行热压烧结。热压烧结操作同上。
在本发明优选的一种具体实施方式中，其中，热压烧结的温度为1550-1800℃，优选的，热压强度为0.5-30MPa。
所述热压强度即施加在单位面积试样上压力值。
例如，温度可以为1550℃、1600℃、1650℃、1700℃、1750℃、1800℃或其之间的任意范围；
热压强度例如可以为0.5MPa、1MPa、1.5MPa、2MPa、2.5MPa、3MPa、3.5MPa、4MPa、4.5MPa、5MPa、5.5MPa、6MPa、6.5MPa、7MPa、7.5MPa、8MPa、8.5MPa、9MPa、9.5MPa、10Mpa、10.5Mpa、11Mpa、11.5Mpa、12Mpa、12.5Mpa、13Mpa、13.5Mpa、14Mpa、14.5Mpa、15Mpa、20Mpa、25Mpa、30Mpa或其之间的任意范围。
本发明提供了一种耐火材料的制备方法，其包括下述步骤：
将颗粒料和细粉混合得到混合料，将所述混合料进行热压烧结得到。
在本发明优选的一种具体实施方式中，其中，所述颗粒料与所述细粉的质量比例为30-65:35-70。
在本发明优选的一种具体实施方式中，其中，所述细粉的粒径≤0.088mm；优选的，所述颗粒料的粒径为0.088-10mm，优选为0.088-8mm。
在本发明优选的一种具体实施方式中，其中，所述热压烧结为将混合料放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型后再放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型和低温装置烧成后再放入高温装置的模具中进行热压烧结。
本发明借助高温高压促进颗粒重排和质点扩散所得到的耐火材料的高温液相量少、组织结构均匀、热震稳定性能好。
本发明提供了一种钢水冶炼用钢包的工作衬，其包括上述所述的耐火材料或者上述所述的制备方法制备得到的耐火材料。
本发明提供了一种铝液冶炼和输运包的工作衬，其包括上述所述的耐火材料或者上述所述的制备方法制备得到的耐火材料。
本发明提供了一种工业窑炉的耐火材料衬体，其包括上述所述的耐火材料或者上述所述的制备方法制备得到的耐火材料。
实施例
本发明对试验中所用到的材料以及试验方法进行一般性和/或具体的描述，在下面的实施例中，如果无其他特别的说明，％表示wt％，即质量百分数。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品，其中，表1为实施例中所用到的原料的来源。
表1实施例中所用到的原料的来源
原料 纯度 生产厂家
板状刚玉粉 Al 2O 3≥97.0％ 青岛安迈铝业有限公司
CA6细粉 Al 2O 3 90.5-92.5％、CaO 7.4-9.0％ 淄博市鲁中耐火材料有限公司
烧结刚玉颗粒料 Al 2O 3≥97.0％ 江苏晶辉耐火材料有限公司
CA6颗粒料 Al 2O 3 90.5-92.5％、CaO 7.4-9.0％ 淄博市鲁中耐火材料有限公司
轻烧氧化镁 MgO≥92.5％ -
CaO·Al 2O 3 Al 2O 3≥64％、CaO≥35％％ 山东圣川新材料有限公司
γ-Al 2O 3粉 Al 2O 3≥96.0％ 山东铝业公司
白刚玉颗粒料 Al 2O 3≥97.5％ 郑州玉发集团
ρ-Al 2O 3细粉 Al 2O 3≥93.5％ 山东铝业公司
12CaO·7Al 2O 3细粉 Al 2O 3≥51％、CaO≥48％％ 山东圣川新材料有限公司
工业氧化铝细粉 Al 2O 3≥96.0％ 山东铝业公司
脱硅锆细粉 ZrO 2+H fO 2≥91％ 山东金太阳锆业有限公司
亚白刚玉颗粒料 Al 2O 3≥96.5％ 洛阳锐石公司
CM2A8颗粒料 Al 2O 3≥84％、CaO≥5.0％，MgO≥8.0％ 淄博市鲁中耐火材料有限公司
活性α-Al 2O 3细粉 Al 2O 3≥97.0％ 青岛安迈铝业有限公司
电熔氧化锆细粉 ZrO 2+H fO 2≥98.5％ 山东金太阳锆业有限公司
C2M2A14颗粒料 Al 2O 3≥87％、CaO≥6.2％，MgO≥4.3％ 淄博市鲁中耐火材料有限公司
板状刚玉颗粒料 Al2O3≥97.0％ 青岛安迈铝业有限公司
白刚玉细粉 Al 2O 3≥97.5％ 郑州玉发集团
高纯镁砂粉 MgO≥96.5％ 营口佳镁耐火材料有限公司
生石灰 CaO≥91.5％ -
单斜氧化锆细粉 ZrO 2+H fO 2≥98.5％ 山东金太阳锆业有限公司
亚白刚玉粉 Al 2O 3≥96.5％ 洛阳锐石公司
实施例1
(1)将白刚玉颗粒600g、活性α-Al 2O 3细粉40g、工业氧化铝细粉100g、CM2A8细粉60g、电熔氧化锆细粉200g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料置于高温装置的模具中进行热压烧结，待温度升高至最高温度为1640℃时施加压力，最大热压强度为6MPa，制得耐蚀损性耐火材料。
将所得到的耐火材料经过粉末XRD分析，即将所测耐火材料进行研磨 至325目以下，然后利用X-射线衍射仪(Bruker:D8ADVANCE)进行扫描。通过对衍射数据进行分析，并与标准PDF卡的匹配，得到相关物相，然后通过对衍射数据的拟合得到相关物相的含量，从而得到物相主要为刚玉、CM2A8、氧化锆，以在所述耐火材料的物相中所占的质量百分比计，刚玉、CM2A8、氧化锆的总量为99.1％，刚玉物相为73.1％、CM2A8物相为6.0％、氧化锆物相为20.0％。
将耐火材料按照标准进行XRF分析，按照GB/T21114-2007进行测定，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括78.17％的Al 2O 3、0.43％的MgO、0.35％的CaO、20.0％的ZrO 2。
对该实施例耐火材料按照GB/T2997-2000进行测定，得到体积密度为3.30g/cm 3。
实施例2
(1)将致密刚玉颗粒300g、板状刚玉颗粒200g、CA6细粉140g、工业氧化铝细粉92g、8.4gCaCO3细粉15g、白刚玉粉160g、脱硅氧化锆细粉100g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料置于高温装置的模具中进行热压烧结；待温度升至1500℃时开始施加压力，边升温边增加压力，温度最高升至1760℃，热压强度最大为2MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6和氧化锆，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CA6和氧化锆的总量为98.18％，刚玉物相为65.1％、CA6物相为23.4％、氧化锆物相为9.68％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括87.12％的Al 2O 3、1.93％的CaO、9.65％的ZrO 2。
按照与实施例1相同的方法进行测定，得到体积密度为3.12g/cm 3。
实施例3
(1)将亚白刚玉颗粒260g、CM2A8颗粒140g、白刚玉粉60g、CM2A8粉100g、C12A7细粉17g、17.5g的氢氧化镁粉、113g的活性α-Al 2O 3粉、 电熔氧化锆粉300g搅拌均匀，颗粒的最大粒径为8mm；
(2)将混合料经压制成型、干燥后置于高温装置的模具中进行热压烧结，温度最高升至1780℃，热压强度最大为0.5MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CM2A8、氧化锆，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CM2A8、氧化锆的总量为98.5％，刚玉物相为32.0％、CM2A8物相为36.5％、氧化锆物相为30％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括64.57％的Al 2O 3、2.94％的MgO、2.01％的CaO、30％的ZrO 2。
按照与实施例1相同的方法进行测定，得到体积密度为3.30g/cm 3。
实施例4
(1)将烧结刚玉颗粒300g、致密刚玉颗粒300g、白刚玉细粉280g、活性α-Al 2O 3粉110g、氢氧化钙细粉13.5g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料料置于高温装置的模具中进行热压烧结，自温度升至1400℃时开始逐渐施加压力，温度最高升至1680℃，热压强度最大为1MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉和CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉和CA6的总量为98.6％，刚玉物相为88.0％，CA6物相为10.6％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括98.99％的Al 2O 3、0.89％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为2.95g/cm 3。
实施例5
(1)将亚白刚玉颗粒500g、CA6细粉73g、白刚玉粉100g，ρ-Al 2O 3粉28g、CaO﹒Al 2O 3细粉40g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料加入适当的水搅拌均匀，浇注成型、干燥后经1500℃预烧处理后置于高温装置的模具中进行热压烧结，待温度升至1770℃时施加压 力，热压强度最大为2MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CA6的总量为96.9％，刚玉物相为74.5％、CA6物相为22.4％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括96.6％的Al 2O 3、1.95％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.12g/cm 3。
实施例6
(1)将板状刚玉颗粒650g、CA6细粉105g、白刚玉粉100g、氢氧化铝粉223g、搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料置于高温装置的模具中进行热压烧结，边升温边加压，温度最高升至1700℃，热压强度最大为14MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CA6的总量为98.1％，刚玉物相为88.0％、CA6物相为10.1％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括98.99％的Al 2O 3、0.75％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.28g/cm 3。
实施例7
(1)将亚白刚玉颗粒500g、C2M2A14细粉100g、CA2细粉为45g、电熔镁砂粉7g、ρ-Al 2O 3粉89g、白刚玉粉260g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料加入适当的水搅拌均匀，振动成型、干燥后经1350℃预烧处理后置于高温装置的模具中进行热压烧结，待温度升至1750℃时施加压力，热压强度最大为1MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、C2M2A14，以在所测耐火材料的物相中所占的质量百分比计，刚玉、C2M2A14的总量为96.2％，刚玉物相为75.0％、C2M2A14物相为21.2％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百 分比计，得到所述耐火材料包括96.3％的Al 2O 3、1.0％的MgO、1.20％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.12g/cm 3。
实施例8
(1)将亚白刚玉颗粒300g、CA6细粉90g、氢氧化钙细粉17g、活性α-Al 2O 3粉138g、ρ-Al 2O 3粉265g、白刚玉粉460g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料经压力成型后干燥，然后至于高温装置中经1450℃处理；将处理后的试样置于高温装置的模具中进行热压烧结，待温度升至1600℃时进行施加压力，边升温边增加压力，温度最高升至1770℃，热压强度最大为3MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CA6的总量为97.1％，刚玉物相为74.7％、CA6物相为22.4％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括96.4％的Al 2O 3、1.91％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.12g/cm 3。
实施例9
(1)将板状刚玉颗粒500g、CM2A8细粉100g、氢氧化钙细粉11g、高纯镁砂粉17.5g、122g工业氧化铝细粉、板状刚玉粉260g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料经常温成型、干燥后置于高温装置的模具中进行热压烧结，待温度升至1550℃时开始施加压力，边升温边增加压力，温度最高升至1740℃，热压强度最大为4MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CM2A8，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CM2A8的总量为95.42％，刚玉物相为73.1％、CM2A8物相为22.32％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括95.7％的Al 2O 3、1.97％的MgO、1.02％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.12g/cm 3。
实施例10
(1)将烧结刚玉颗粒260g、CA6颗粒140g、亚白刚玉细粉120g、Ca(OH) 2细粉55g、板状刚玉粉200g、ρ-Al 2O 3细粉245g搅拌均匀，最大粒径为6mm；
(2)将混合料经常温压制成型及1500℃预烧处理，然后置于高温装置的模具中，边升温边施加压力，温度最高升至1750℃，热压强度最大为7MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CA6的总量为98.8％，刚玉物相为36.8％、CA6物相为62.0％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括93.7％的Al 2O 3、5.20％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.25g/cm 3。
实施例11
(1)将板状刚玉颗粒195g、CM2A8颗粒105g、活性α-Al 2O 3粉70g、CM2A8细粉280g、四方氧化锆细粉100g、电熔氧化锆细粉250g搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料经常温成型后置于高温装置的模具中进行热压烧结，边升温边施加压力，温度最高升至1550℃，热压强度最大为30MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CM2A8、氧化锆，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CM2A8、氧化锆的总量为99.6％，刚玉物相为26.5％、CM2A8物相为38.1％、氧化锆物相为35％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括59.5％的Al 2O 3、3.01％的MgO、2.03％的CaO和35％的ZrO 2。
按照与实施例1相同的方法进行测定，得到体积密度为3.45g/cm 3。
实施例12
(1)将亚白刚玉颗粒350g、烧结刚玉颗粒300g、单斜氧化锆细粉175g、CM2A8细粉52.5g、氢氧化铝粉188g、搅拌均匀，颗粒的最大粒径为3mm；
(2)将混合料置于高温炉装置的模具中进行热压烧结，待温度升高至1350℃时开始施加压力，边升温边增加压力，温度最高升至1600℃，热压强度最大为15MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CM2A8和氧化锆，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CA6和氧化锆的总量为97.15％，刚玉物相为75.4％、CM2A8物相为5.25％、氧化锆物相为16.5％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括80.8％的Al 2O 3、0.30％的CaO、0.43％的MgO、16.9％的ZrO 2。
按照与实施例1相同的方法进行测定，得到体积密度为3.26g/cm 3。
实施例13
(1)将烧结刚玉颗粒195g、CA6颗粒105g、工业氧化铝细粉100g、ρ-Al 2O 3粉138.5g、CA6细粉460g、氢氧化钙粉11.5g搅拌均匀，颗粒的最大粒径为8mm；
(2)将混合料常温成型、干燥，经1500℃处理后置于高温炉的模具中进行热压烧结，温度最高升至1700℃，热压强度最大为21MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉和CA6的总量为97.7％，刚玉物相为31.2％，CA6物相为66.5％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括93.1％的Al 2O 3、5.58％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.25g/cm 3。
实施例14
(1)将烧结刚玉颗粒300g、工业氧化铝细粉460g、CA6细粉140g、 氢氧化钙粉11.5g、γ-Al 2O 3粉93g、搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料料置于高温装置的模具中进行热压烧结，温度最高升至1650℃，热压强度最大为8MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉和CA6的总量为95.4％，刚玉物相为75.1％，CA6物相为20.3％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括96.1％的Al 2O 3、1.94％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为2.90g/cm 3。
实施例15
(1)将烧结刚玉颗粒260g、CM2A8颗粒140g、工业氧化铝细粉40g、ρ-Al 2O 3粉83g、CM2A8细粉480g搅拌均匀，颗粒的最大粒径为10mm；
(2)将混合料料置于高温炉的模具中进行热压烧结，温度最高升至1650℃，热压强度最大为4MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CM2A8，以在所测耐火材料的物相中所占的质量百分比计，刚玉和CM2A8的总量为98.8％，刚玉物相为36.8％，CM2A8物相为62％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括90.1％的Al 2O 3、5.20％的MgO、3.60％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为2.90g/cm 3。
实施例16
(1)将烧结刚玉颗粒195g、CM2A8颗粒105g、工业氧化铝细粉100g、ρ-Al 2O 3细粉40g、CM2A8细粉560g搅拌均匀，颗粒的最大粒径为1mm；
(2)将混合料置于高温炉的模具中直接进行热压烧结，最高温度为1800℃，热压强度为2MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CM2A8，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CM2A8的总量为98.3％，刚玉物相为31.8％、CM2A8物相为66.5％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括89.3％的Al 2O 3、5.58％的MgO、3.88％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.65g/cm 3。
实施例17
(1)将烧结刚玉颗粒300g、工业氧化铝细粉585g、ρ-Al 2O 3细粉40g、氢氧化钙细粉45g、电熔镁砂48g搅拌均匀，颗粒的最大粒径为1mm；
(2)将混合料常温成型、干燥，经1450℃处理后置于高温装置的模具中进行热压烧结，最高温度为1720℃，热压强度为3MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CM2A8、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CM2A8的总量为90.0％，刚玉物相为44.0％、CM2A8物相为22.6％、CA6物相为23.4％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括90.8％的Al 2O 3、4.28％的MgO、3.13％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为2.93g/cm 3。
实施例18
(1)将白刚玉颗粒650g、CA6细粉105g、白刚玉粉250g、搅拌均匀，颗粒的最大粒径为5mm；
(2)将混合料置于高温装置的模具中进行热压烧结，边升温边加压，温度最高升至1715℃，热压强度最大为7.5MPa，制得耐蚀损性耐火材料。
按照与实施例1相同的方法进行分析，得到物相主要为刚玉、CA6，以在所测耐火材料的物相中所占的质量百分比计，刚玉、CA6的总量为99.53％，刚玉物相为89.50％、CA6物相为10.3％。
按照与实施例1相同的方法进行分析，以在所述耐火材料所占的质量百分比计，得到所述耐火材料包括98.99％的Al 2O 3、0.84％的CaO。
按照与实施例1相同的方法进行测定，得到体积密度为3.25g/cm 3。
对比例1
对比例1和实施例1的区别在于，对比例1使用的是常规的制备方法，即采用中国专利申请CN107500747A中实施例1的方法进行得到耐火材料。
按照与实施例1相同的方法进行分析，以在所述耐火材料中所占的质量百分比计，所得到的耐火材料的化学成分包括Al 2O 3 92.11％、CaO7.02％。
按照与实施例1相同的方法进行分析，所述对比例1的物相主要为CA6、刚玉、CaO·Al 2O 3和CaO·2Al 2O 3，以在所述耐火材料的物相所占的质量百分比计，CA6物相为69.1％、刚玉物相为24.2％、CaO·Al 2O 3物相为2.30％、CaO·2Al 2O 3物相为2.31％。
按照与实施例1相同的方法进行分析，所述对比例1的体积密度为3.05g/cm 3。
表2实施例及对比例所用到的原料及其所得到的耐火材料表
Figure PCTCN2022091728-appb-000001
Figure PCTCN2022091728-appb-000002
实验例1动态渣侵蚀实验
动态渣侵蚀实验采用实施例1所得到的耐火材料和对比例1所得到的耐火材料试样进行对比。
做动态渣侵的试样需要较长的长度，以便能够固定在转动轴上。鉴于实施例1所得到的耐火材料的体积密度较高，刚玉相含量高且硬度大，很难钻成φ15mm圆柱状试样，仅切割成方形条状。作为侵蚀速率的测量，以对边的尺寸为准，如此，将试样切割成方形条状不影响最终结果的准确性。作为对比，将对比例1的浇注料浇注成同样尺寸的试样。
动态渣侵蚀实验的条件为：脱氧方式采用金属铝脱氧，实验温度为1600℃，氩气气氛，渣系采用CaO-Al 2O 3-SiO 2系，钢渣成分为CaO51％，Al 2O 330％，SiO 211％，MgO8％，CaO/SiO 2为4.6。
将对比例1的浇注料以及实施例1所述的耐火材料分别利用高温粘结剂粘结在上面的电动机上，控制旋转速度为10周/分钟，其实验结果分别如图1A和图1B所示。
从图1A和图1B可以看出，在旋转8分钟时，浸在钢渣中的对比例1的浇注料试样已经溃散，而实施例1的耐火材料变化不大，圆整度仍然非常明显，基本上没有太大变化。剖开试样，利用游标卡尺测定未反应界面的宽度表明，其损毁了0.2～0.5mm，表明实施例1所得到的耐火材料的耐侵蚀性是非常出色的。
实验例2静态渣侵蚀实验
静态渣侵蚀实验采用坩埚法，其中，图2A为进行钢水冶炼的静态坩埚法示意图。
实施例1的试样是首先热压成φ45mm试样，再从中钻出φ30mm×40mm凹坑。将对比例1的浇注料也浇注成φ45mm试样，内部凹坑尺寸为φ30mm×40mm。实验条件为1600℃，氩气气氛，采用金属铝脱氧。渣系采用CaO-Al 2O 3-SiO 2系，钢渣成分为CaO 51％，Al 2O 3 30％，SiO 2 11％，MgO 8％，CaO/SiO 2为4.6，静态渣侵蚀结果如图2B所示，其中，a、b和c分别为对比例1浇注料在30min、40min和50min的轮廓结构，d、e、f分别为实施例1试样在30min、40min和50min的轮廓结构。
从图2B中可以看出，对于对比例1浇注料而言，40min时有些部位已经被熔渣完全渗透且侵蚀，试样溃散；尽管有些部分侵蚀厚度显示为270μm，但是熔渣已经完全渗透，这是由传统耐火材料的结构和性能导致的。因传统材料的结构不均匀性，往往是整体都很好，但有些部位已经承受不住了。而本发明的实施例1试样则表现出非常好的均匀性，结构非常完整。
此外，图2C为对比例1的浇注料和本专利实施例1试样的显微结构对比，a、b和c分别为对比例1浇注料在30min、40min和50min时的显微结构，d、e、f分别为实施例1试样在30min、40min和50min时的显微结构。从微结构中也可看出，对比例1的浇注料的结构是很不均匀的，熔渣可以沿 着孔洞比较多的地方渗透很深，而本专利实施例1的变质层却非常薄，且很均匀。这也显示出本发明试样的性能出色。
实验例3熔渣侵蚀以及热震稳定性的实验
将实施例1-17以及对比例1所得到的耐火材料进行渣侵蚀情况以及热震稳定性的实验，其中，关于熔渣侵蚀情况的测定：首先将实验后的坩埚沿中间面切开，在坩埚壁上取样并进行电镜观察和测量，从而测得熔渣侵蚀情况。热震稳定性实验按照GB/T 30873-2014测定，其结果如表3所示。
表3实验数据
  渣侵蚀情况，μm/40min 热震稳定性，次
实施例1 100μm 10
实施例2 130μm 16
实施例3 124μm 14
实施例4 155μm 12
实施例5 142μm 13
实施例6 134μm 12
实施例7 147μm 10
实施例8 160μm 11
实施例9 158μm 10
实施例10 154μm 13
实施例11 133μm 10
实施例12 117μm 8
实施例13 165μm 12
实施例14 170μm 17
实施例15 183μm 16
实施例16 138μm 5
实施例17 210μm 15
实施例18 128μm 12
对比例1 7.5mm 15
对耐火材料来讲，其能否应用及性能评价除与其耐熔渣侵蚀性有关外，还需要考虑耐火材料在温度急冷急热条件下的热震稳定性；如果热震稳定性不好，则使用中可能出现裂纹，影响材料使用性能。
对于耐侵蚀性而言，在相同体积密度的情况下，ZrO 2的加入是有利的；相对于CA6、C2M2A8、CM2A8，刚玉的耐侵蚀性较好。对于成分相同情况下，体积密度大的耐火材料的耐侵蚀性比较好。
对于热震稳定性，ZrO 2的加入是有利的，CA6的加入比加入同等质量的 刚玉、C2M2A8、CM2A8的耐火材料的热震稳定性好；在成分相同情况下，体积密度小，则热震稳定性相对要好些。
另外，还需考虑耐火材料的性价比，比如添加氧化锆的耐火材料的抵抗熔渣侵蚀性和热震稳定性都很好，而且添加量多的情况下，其性能也较出色，但是氧化锆比较昂贵，因此，对于本发明的实施例，其性能优劣是综合比较的结果。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。

Claims (22)

  1. 一种耐蚀损性耐火材料，所述耐火材料的物相包括刚玉和选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上的物相。
  2. 根据权利要求1所述的耐火材料，其中，以在所述耐火材料的物相所占的质量百分比计，刚玉以及选自CA6、C2M2A14、CM2A8和ZrO 2中的一种或两种以上的物相之和≥90％；
    优选的，刚玉物相为26.5-89.5％，优选为32-89.5％，进一步优选为32.0-88.0％；
    CA6+C2M2A14+CM2A8物相总量之和为5.25-66.5％，优选为5.25-62.0％，进一步优选6.0-62.0％；以及
    ZrO 2物相为0-35％，优选为0-30％。
  3. 根据权利要求1或2所述的耐火材料，其中，以在所述耐火材料中所占的质量百分比计，促烧结的杂质组分含量≤1.5％，优选≤1.0％。
  4. 根据权利要求1-3中任一项所述的耐火材料，其中，所述耐火材料的化学成分包括Al 2O 3、CaO、MgO和ZrO 2，以在所述耐火材料中所占的质量百分比计，所述Al 2O 3为59.5-98.99％，优选为64.57-98.99％；所述CaO为0.30-5.58％，优选为0.35-5.58％，进一步优选为0.30-5.20％或0.35-5.20％；所述MgO为0-5.58％以及所述ZrO 2为0-35％。
  5. 根据权利要求1-4中任一项所述的耐火材料，其中，所述耐火材料的体积密度为2.90-3.65g/cm 3，优选为2.95-3.45g/cm 3，进一步优选为2.95-3.30g/cm 3。
  6. 根据权利要求1-5中任一项所述的耐火材料，其中，所述耐火材料通过包含下述步骤的方法制备得到：
    将颗粒料和细粉混合得到混合料，将所述混合料进行热压烧结得到。
  7. 根据权利要求6所述的耐火材料，其中，所述颗粒料与所述细粉的质量比例为30-65:35-70。
  8. 根据权利要求6或7所述的耐火材料，其中，所述颗粒料包括刚玉颗粒料和混合颗粒料，优选的，以在颗粒料中所占的质量百分比计，所述刚玉颗粒料为65-100％，所述混合颗粒料为0-35％；
    优选的，所述混合颗粒料选自CA6颗粒料、C2M2A14颗粒料和CM2A8颗粒料中的一种或两种以上；
    优选的，所述刚玉颗粒料选自板状刚玉颗粒料、烧结刚玉颗粒料、白刚玉颗粒料、致密刚玉颗粒和亚白刚玉颗粒料中的一种或两种以上。
  9. 根据权利要求6-8中任一项所述的耐火材料，其中，所述细粉包括Al 2O 3-CaO-MgO系细粉和含ZrO 2的细粉，优选的，以在细粉中所占的质量百分比计，所述Al 2O 3-CaO-MgO系细粉为50-100％，所述含ZrO 2的细粉为0-50％；
    优选的，所述Al 2O 3-CaO-MgO系细粉包括含Al 2O 3的细粉以及选自CA6、C2M2A14、CM2A8和MgO-CaO系细粉中的一种或两种以上的细粉；
    优选的，所述MgO-CaO系细粉为含MgO的细粉和/或含CaO的细粉；
    优选的，所述含Al 2O 3的细粉选自活性α-Al 2O 3粉、γ-Al 2O 3粉、ρ-Al 2O 3粉、氢氧化铝、工业氧化铝、白刚玉粉、烧结刚玉粉和板状刚玉粉中的一种或两种以上的细粉；
    优选的，所述含MgO的细粉选自碳酸镁、轻烧氧化镁、水镁石、氢氧化镁、氯化镁、高纯氧化镁和电熔氧化镁中的一种或两种以上的细粉；
    优选的，所述含CaO的细粉选自生石灰、石灰石、氢氧化钙、CaO·Al 2O 3、CaO·2Al 2O 3、12CaO·7Al 2O 3、CA6、C2M2A14和CM2A8中一种或两种以上；
    优选的，所述含ZrO 2的细粉选自单斜氧化锆、四方氧化锆、脱硅锆和电熔氧化锆中的一种或两种以上。
  10. 根据权利要求6-9中任一项所述的耐火材料，其中，所述细粉的粒径≤0.088mm；优选的，所述颗粒料的粒径为0.088-10mm,优选为0.088-8mm。
  11. 根据权利要求6-10中任一项所述的耐火材料，其中，所述热压烧结为将混合料放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型后再放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型和低温预烧结后进行热压烧结。
  12. 根据权利要求11所述的耐火材料，其中，热压烧结的温度为1550-1800℃，优选的，热压强度为0.5-30MPa。
  13. 一种耐火材料的制备方法，其包括下述步骤：
    将颗粒料和细粉混合得到混合料，将所述混合料进行热压烧结得到。
  14. 根据权利要求13所述的制备方法，其中，所述颗粒料与所述细粉的质量比例为30-65:35-70。
  15. 根据权利要求13或14所述的制备方法，其中，所述颗粒料包括刚玉颗粒料和混合颗粒料，优选的，以在颗粒料中所占的质量百分比计，所述刚玉颗粒料为65-100％，所述混合颗粒料为0-35％；
    优选的，所述混合颗粒料为CA6颗粒料、C2M2A14颗粒料和CM2A8颗粒料中的一种或两种以上；
    优选的，所述刚玉颗粒料选自板状刚玉、烧结刚玉、白刚玉、致密刚玉和亚白刚玉中的一种或两种以上。
  16. 根据权利要求13-15中任一项所述的制备方法，其中，所述细粉包括Al 2O 3-CaO-MgO系细粉和含ZrO 2的细粉，优选的，以在细粉中所占的质量百分比计，所述Al 2O 3-CaO-MgO系细粉为50-100％，所述含ZrO 2的细粉为0-50％；
    优选的，所述Al 2O 3-CaO-MgO系细粉包括含Al 2O 3的细粉以及选自CA6、C2M2A14、CM2A8和MgO-CaO系细粉中的一种或两种以上的细粉；
    优选的，所述MgO-CaO系细粉为含MgO的细粉和/或含CaO的细粉；
    优选的，所述含Al 2O 3的细粉选自活性α-Al 2O 3粉、γ-Al 2O 3粉、ρ-Al 2O 3粉、氢氧化铝、工业氧化铝、白刚玉粉、烧结刚玉粉和板状刚玉粉中的一种或两种以上的细粉；
    优选的，所述含MgO的细粉选自碳酸镁、轻烧氧化镁、水镁石、氢氧化镁、氯化镁、烧结氧化镁和电熔氧化镁中的一种或两种以上的细粉；
    优选的，所述含CaO的细粉选自生石灰、石灰石、氢氧化钙、CaO·Al 2O 3、CaO·2Al 2O 3、12CaO·7Al 2O 3、CA6、C2M2A14和CM2A8中一种或两种以上；
    优选的，所述含ZrO 2的细粉选自单斜氧化锆、四方氧化锆、脱硅锆和电熔氧化锆中的一种或两种以上。
  17. 根据权利要求13-16中任一项所述的制备方法，其中，所述细粉的粒径≤0.088mm；优选的，所述颗粒料的粒径为0.088-10mm，优选为0.088-8mm。
  18. 根据权利要求13-17中任一项所述的制备方法，其中，所述热压烧结为将混合料放入高温装置的模具中进行热压烧结或者将所述混合料经常温 成型后再放入高温装置的模具中进行热压烧结或者将所述混合料经常温成型和低温预烧结后再放入高温装置的模具中进行热压烧结。
  19. 根据权利要求18所述的制备方法，其中，所述热压烧结的温度为1550-1800℃，优选的，热压强度为0.5-30MPa。
  20. 一种钢水冶炼用钢包的工作衬，其包括权利要求1-12中任一项所述的耐火材料或者权利要求13-19中任一项所述的制备方法制备得到的耐火材料。
  21. 一种铝液冶炼和输运包的工作衬，其包括权利要求1-12中任一项所述的耐火材料或者权利要求13-19中任一项所述的制备方法制备得到的耐火材料。
  22. 一种工业窑炉的耐火材料衬体，其包括权利要求1-12中任一项所述的耐火材料或者权利要求13-19中任一项所述的制备方法制备得到的耐火材料。
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