CORROSION-RESISTANT REFRACTORY MATERIAL, PREPARATION METHOD THEREFOR, AND USE THEREOF

Abstract

Disclosed in the present invention are a corrosion-resistant refractory material, preparation method therefor, and the use thereof. In the corrosion-resistant refractory material, a material phase of the refractory material comprises corundum and one or more material phases selected from CA6, C2M2A14, CM2A8, and ZrO.sub.2. The refractory material has low a low amount of a high-temperature liquid phase, a uniform pore structure, and good thermal shock stability; can be widely used in steel-making production lines and also in the refractory linings of rotary kilns, and has good erosion resistance and low thermal conductivity, and the performance thereof is obviously superior to that of many existing refractory materials such as silico carbide-mullite bricks and magnesia-alumina spinel bricks.

Claims

1. A corrosion-resistant refractory material, wherein the phase of the refractory material comprises corundum and one or two or more selected from the group consisting of: CA6, C2M2A14, CM2A8 and ZrO.sub.2.

2. The refractory material according to claim 1, wherein based on the mass percentage of the phase of the refractory material, the total phase content of the corundum and one or two or more selected from CA6, C2M2A14, CM2A8 and ZrO.sub.2 is ?90%; preferably the phase content of corundum is 26.5-89.5%, preferably 32-89.5%, more preferably 32.0-88.0%; the total phase content of CA6+C2M2A14+CM2A8 is 5.25-66.5%, preferably 5.25-62.0%, more preferably 6.0-62.0%; and the phase content of ZrO.sub.2 is 0-35%, preferably 0-30%.

3. The refractory material according to claim 1, wherein based on the mass percentage in the refractory material, the content of sintering-promoting impurity components is ?1.5%, preferably ?1.0%.

4. The refractory material according to claim 1, wherein the chemical composition of the refractory material comprises Al.sub.2O.sub.3, CaO, MgO and ZrO.sub.2, based on the mass percentage in the refractory material, the Al.sub.2O.sub.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.sub.2 is 0-35%.

5. The refractory material according to claim 1, wherein the bulk density of the refractory material is 2.90-3.65 g/cm.sup.3, preferably 2.95-3.45 g/cm.sup.3, more preferably 2.95-3.30 g/cm.sup.3.

6. The refractory material according to claim 1, wherein the refractory material is prepared by a method comprising the following steps: mixing a granular material and a fine powder to obtain a mixed material, then subjecting the mixed material to hot-pressed sintering to obtain the refractory material.

7. The refractory material according to claim 6, wherein the mass ratio of the granular material to the fine powder is 30-65:35-70.

8. The refractory material according to claim 6, wherein the granular material comprises corundum granular material and a mixed granular material, preferably based on the mass percentage in the granular material, the corundum granular material is 65-100%, and the mixed granular material is 0-35%; preferably the mixed granular material is one or two or more selected from the group consisting of: CA6 granular material, C2M2A14 granular material, and CM2A8 granular material; preferably the corundum granular material is one or two or more selected from the group consisting of: tabular corundum granular material, sintered corundum granular material, white corundum granular material, dense corundum granular material, and sub-white corundum granular material.

9. The refractory material according to claim 6, wherein the fine powder comprises Al.sub.2O.sub.3CaOMgO system fine powder and ZrO.sub.2-containing fine powder, preferably based on the mass percentage in the fine powder, the Al.sub.2O.sub.3CaOMgO system fine powder is 50-100%, and the ZrO.sub.2-containing fine powder is 0-50%; preferably the Al.sub.2O.sub.3CaOMgO system fine powder comprises Al.sub.2O.sub.3-containing fine powder and one or two or more fine powders selected from CA6 fine powder, C2M2A14 fine powder, CM2A8 fine powder and MgOCaO system fine powder; preferably the MgOCaO system fine powder is MgO-containing fine powder and/or CaO-containing fine powder; preferably the Al.sub.2O.sub.3-containing fine powder is one or two or more selected from the group consisting of: active ?-Al.sub.2O.sub.3 fine powder, ?-Al.sub.2O.sub.3 fine powder, ?-Al.sub.2O.sub.3 fine powder, aluminum hydroxide fine powder, industrial alumina fine powder, white corundum fine powder, sintered corundum fine powder, and tabular corundum fine powder; preferably the MgO-containing fine powder is one or two or more selected from the group consisting of: magnesium carbonate fine powder, light-calcined magnesia fine powder, brucite fine powder, magnesium hydroxide fine powder, magnesium chloride fine powder, high-purity magnesia fine powder, and fused magnesia fine powder; preferably the CaO-containing fine powder is one or two or more selected from the group consisting of: quicklime fine powder, limestone fine powder, calcium hydroxide fine powder, CaO.Math.Al.sub.2O.sub.3 fine powder, CaO.Math.2A120; fine powder, 12CaO.Math.7Al.sub.2O.sub.3 fine powder, CA6 fine powder, C2M2A14 fine powder and CM2A8 fine powder; preferably the ZrO.sub.2-containing fine powder is one or two or more selected from the group consisting of: monoclinic zirconia fine powder, tetragonal zirconia fine powder, desiliconized zirconium fine powder, and fused zirconia fine powder.

10. The refractory material according to claim 6, wherein the particle size of the fine powder is ?0.088 mm; preferably the particle size of the granular material is 0.088-10 mm, more preferably 0.088-8 mm.

11. The refractory material according to claim 6, wherein the hot-pressed sintering is performed by putting the mixed material into a mold of a high temperature device for hot-pressed sintering; or molding the mixed material at normal temperature, and then putting it into a mold of a high temperature device for hot-pressed sintering; or molding the mixed material at normal temperature, and presintering it at low temperature, and then putting it into a mold of a high temperature device for hot-pressed sintering.

12. The refractory material according to claim 11, wherein the temperature of the hot-pressed sintering is 1550-1800? C.; preferably the strength of the hot-pressed sintering is 0.5-30 MPa.

13. A preparation method for refractory material, comprising the following steps: mixing a granular material and a fine powder to obtain a mixed material, then subjecting the mixed material to hot-pressed sintering to obtain the refractory material.

14. The preparation method according to claim 13, wherein the mass ratio of the granular material to the fine powder is 30-65:35-70.

15. The preparation method according to claim 13, wherein the granular material comprises corundum granular material and a mixed granular material, preferably based on the mass percentage in the granular material, the corundum granular material is 65-100%, and the mixed granular material is 0-35%; preferably the mixed granular material is one or two or more selected from the group consisting of: CA6 granular material, C2M2A14 granular material, and CM2A8 granular material; preferably the corundum granular material is one or two or more selected from the group consisting of: tabular corundum granular material, sintered corundum granular material, white corundum granular material, dense corundum granular material, and sub-white corundum granular material.

16. The preparation method according to claim 13, wherein the fine powder comprises Al.sub.2O.sub.3CaOMgO system fine powder and ZrO.sub.2-containing fine powder, preferably based on the mass percentage in the fine powder, the Al.sub.2O.sub.3CaOMgO system fine powder is 50-100%, and the ZrO.sub.2-containing fine powder is 0-50%; preferably the Al.sub.2O.sub.3CaOMgO system fine powder comprises Al.sub.2O.sub.3-containing fine powder and one or more fine powders selected from CA6 fine powder, C2M2A14 fine powder, CM2A8 fine powder and MgOCaO system fine powder; preferably the MgOCaO system fine powder is MgO-containing fine powder and/or CaO-containing fine powder; preferably the Al.sub.2O.sub.3-containing fine powder is one or two or more selected from the group consisting of: active ?-Al.sub.2O.sub.3 fine powder, ?-Al.sub.2O.sub.3 fine powder, ?-Al.sub.2O.sub.3 fine powder, aluminum hydroxide fine powder, industrial alumina fine powder, white corundum fine powder, sintered corundum fine powder, and tabular corundum fine powder; preferably the MgO-containing fine powder is one or two or more selected from the group consisting of: magnesium carbonate fine powder, light-calcined magnesia fine powder, brucite fine powder, magnesium hydroxide fine powder, magnesium chloride fine powder, high-purity magnesia fine powder, and fused magnesia fine powder; preferably the CaO-containing fine powder is one or two or more selected from the group consisting of: quicklime fine powder, limestone fine powder, calcium hydroxide fine powder, CaO.Math.Al.sub.2O.sub.3 fine powder, CaO.Math.2Al.sub.2O.sub.3 fine powder, 12CaO.Math.7Al.sub.2O.sub.3 fine powder, CA6 fine powder, C2M2A14 fine powder and CM2A8 fine powder; preferably the ZrO.sub.2-containing fine powder is one or two or more selected from the group consisting of: monoclinic zirconia fine powder, tetragonal zirconia fine powder, desiliconized zirconium fine powder, and fused zirconia fine powder.

17. The preparation method according to claim 13, wherein the particle size of the fine powder is ?0.088 mm; preferably the particle size of the granular material is 0.088-10 mm, preferably 0.088-8 mm.

18. The preparation method according to claim 13, wherein the hot-pressed sintering is performed by putting the mixed material into a mold of a high temperature device for hot-pressed sintering; or molding the mixed material at normal temperature, and then putting it into a mold of a high temperature device for hot-pressed sintering; or molding the mixed material at normal temperature, and presintering it at low temperature, and then putting it into a mold of a high temperature device for hot-pressed sintering.

19. The preparation method according to claim 18, wherein the temperature of the hot-pressed sintering is 1550-1800? C.; preferably the strength of the hot-pressed sintering is 0.5-30 MPa.

20. A working lining of a ladle for molten steel smelting, or working lining for molten aluminum smelting and transporting ladles, or refractory lining for industrial furnaces, wherein it comprises the refractory material according to claim 1, or a refractory material prepared by a preparation method comprising mixing a granular material and a fine powder to obtain a mixed material, then subjecting the mixed material to hot-pressed sintering to obtain the refractory material.

21. (canceled)

22. (canceled)

Description

BRIEF DESCRIPTION OF DRAWINGS

[0080] FIG. 1A is a schematic diagram of the effect of the castable obtained in Comparative Example 1 after dynamic rotating slag erosion on the castable obtained in proportion 1.

[0081] FIG. 1B is a schematic diagram of the sample effect of the refractory material described in Example 1 after dynamic rotating slag erosion.

[0082] FIG. 2A is a schematic diagram of the static crucible method for molten steel smelting in Experiment Example 2, wherein 1 is slag, 2 is a alumina crucible, 3 is steel, 4 is aluminum, and 5 is a refractory crucible.

[0083] FIG. 2B shows the effect of the erosion of the castable obtained in Comparative Example 1 and the refractory material described in Example 1 over time after molten steel smelting by the static crucible method, a. b, and c represent the contour structures of the castable obtained in Comparative Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively, while d, e, and f represent the contour structures of the refractory obtained for example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively.

[0084] FIG. 2C is a schematic diagram of the microstructure comparison effect between the castable obtained in Comparative Example 1 and the refractory material described in Example 1.

DETAILED DESCRIPTION OF THE INVENTION

[0085] The following is a detailed explanation of the present application in conjunction with the embodiments described in the accompanying drawings, where the same numbers in all drawings represent the same features. Although specific embodiments of the present application are shown in the accompanying drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described here. On the contrary, these embodiments are provided for thoroughly understanding of the present application and to fully convey the scope of the present application to those skilled in the art.

[0086] It should be noted that certain terms are used in the specification and claims to refer to specific components. It should be understood by those skilled in the art that they may use different terms to refer to the same component. This specification and claims do not use differences in nouns as a way to distinguish components, but rather use differences in the function of components as a criterion for distinguishing components. The words comprises or includes mentioned throughout the entire specification and claims are open-ended terms, they should be interpreted as including but not limited to. The subsequent description of the specification is a preferred embodiment for implementing the present application. However, the description is intended as the general principles of the specification and is not intended to limit the scope of the present application. The scope of protection of the present application shall be determined by the appended claims.

[0087] The present application provides a corrosion-resistant refractory material, wherein the phase of the refractory material comprises corundum and one or two or more selected from the group consisting of: CA6, C2M2A14, CM2A8, and ZrO.sub.2.

[0088] The phase of the refractory material is determined by XRD, for example, by grinding the measured material to below 325 mesh, and then scanning it using an X-ray diffractometer. The diffraction data are analyzed and matched with a standard PDF cards to obtain the relevant phases. Then, the content of the relevant phases is obtained by fitting the diffraction data.

[0089] Regarding the ZrO.sub.2 phase, due to the coexistence of HrO.sub.2 and ZrO.sub.2, it is difficult to separate and the crystal forms are similar. Therefore, the following explanation is made.

[0090] (1) H.sub.fO.sub.2 phase is included in ZrO.sub.2.

[0091] (2) Due to different temperatures and processes, as well as uneven composition distribution (it is impossible to achieve absolute uniformity), ZrO.sub.2CaO solid solution, ZrO.sub.2MgO solid solution, CaOZrO.sub.2, MgOZrO.sub.2 and other phases may appear in the final product. In the case of the appearance of ZrO.sub.2CaO solid solution, ZrO.sub.2MgO solid solution, CaOZrO.sub.2, MgOZrO.sub.2 and other phases, the ZrO.sub.2 content is firstly corrected by combining the XRF results. And then this ZrO.sub.2 content is converted into zirconia phase, converting CaO, MgO, etc. that have been solidly dissolved or bound in the form of CaO.Math.ZrO.sub.2, MgO.Math.ZrO.sub.2, etc. into CA6 and CMA (this CaO, MgO content is first converted into CA6 and MA, and then into CA6, CMA, etc. based on temperature or CaOMgOAl.sub.2O; system composition), then normalizing all phases to 100% and calculating the percentage of each phase.

[0092] Regarding the content of ZrO.sub.2 in the chemical composition, as it is difficult to separate HrO.sub.2 due to its symbiosis with ZrO.sub.2. Therefore, in the XRF of this application, the HrO.sub.2 content is calculated in the ZrO.sub.2 content.

[0093] In a preferred embodiment of the present application, wherein the total phase content of corundum and one or two or more selected from CA6, C2M2A14, CM2A8, and ZrO.sub.2 is greater than or equal to 90% based on the mass percentage of the phase in the refractory material: [0094] preferably, the phase content of corundum is 26.5-89.5%, preferably 32-89.5%, and more preferably 32.0-88.0%:

[0095] The total phase content of CA6+C2M2A14+CM2A8 is 5.25-66.5%, preferably 5.25-62.0%, and more preferably 6.0-62.0%; and the phase content of ZrO.sub.2 is 0-35%, preferably 0-30%.

[0096] For example, based on the mass percentage of the phases in the refractory material, the total phase content can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, etc.

[0097] The phase content of corundum is 26.5%, 32%, 34.75%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 89.5%, etc.

[0098] The total phase content 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.

[0099] The phase content of ZrO.sub.2 can be 0, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, etc.

[0100] Among them, the total phase content of CA6+C2M2A14+CM2A8 refers to the content of CA6 when only CA6 is present in the phase, or the content of C2M2A14 or CM2A8 phase when only C2M2A14 or CM2A8 phase is present.

[0101] When CA6 and C2M2A14 are present in the phase, it refers to the total content of the two phases. When C2M2A14 and CM2A8 are present in the phase, it refers to the total content of the two phases. When there are CA6 and CM2A8 in the phase, it refers to the total content of the two phases.

[0102] When there are CA6, C2M2A14, and CM2A8 phases in the phase, it refers to the total content of the three phases.

[0103] In a preferred embodiment of the present application, the content of sintering-promoting impurity components is ?1.5%, preferably ?1.0% based on the mass percentage in the refractory material.

[0104] For example, based on the mass percentage in the refractory material, the content of sintering-promoting impurity components is 1.5%, 1.4%, 13%, 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 in between.

[0105] The promoting sintering impurity components are SiO.sub.2, TiO.sub.2, Fe.sub.2O.sub.3, and R.sub.2O, wherein R.sub.2O refers to the oxide of the alkali metal, and the promoting sintering impurity components refer to the chemical composition.

[0106] In a preferred embodiment of the present application, wherein the chemical composition of the refractory material comprises Al.sub.2O.sub.3, CaO, MgO, and ZrO.sub.2, based on the mass percentage in the refractory material, the Al.sub.2O.sub.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.sub.2 is 0-35%.

[0107] For example, based on the mass percentage in the refractory material, the Al.sub.2O.sub.3 can be 59.5%, 61.45%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98.5%, 98.99% or any range between them.

[0108] The CaO can be 0.30%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4.5%, 5%, 5.58% or any range between them.

[0109] 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 between them.

[0110] The ZrO.sub.2 can be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or any range in between.

[0111] The chemical composition of the refractory material is determined by fluorescence analysis, that is XRF in accordance with GB/T21114-2007.

[0112] In a preferred embodiment of the present application, the bulk density of the refractory material is 2.90-3.65 g/cm.sup.3, preferably 2.95-3.45 g/cm.sup.3, and more preferably 2.95-3.30 g/cm.sup.3.

[0113] For example, the bulk density of the refractory material can be 2.90 g/cm.sup.3, 2.91 g/cm.sup.3, 2.92 g/cm.sup.3, 2.93 g/cm.sup.3, 2.94 g/cm.sup.3, 2.95 g/cm.sup.3, 2.96 g/cm.sup.3, 2.97 g/cm.sup.3, 2.98 g/cm.sup.3, 2.99 g/cm.sup.3, 3.00 g/cm.sup.3, 3.05 g/cm.sup.3, 3.10 g/cm.sup.3, 3.15 g/cm.sup.3, 3.20 g/cm.sup.3, 3.25 g/cm.sup.3, 3.30 g/cm.sup.3, 3.35 g/cm.sup.3, 3.40 g/cm.sup.3, 3.45 g/cm.sup.3, 3.50 g/cm.sup.3, 3.55 g/cm.sup.3, 3.60 g/cm.sup.3, 3.65 g/cm.sup.3 or any range between them.

[0114] The bulk density of the refractory material is measured in accordance with GB/T2997-2000.

[0115] In a preferred embodiment of the present application, the refractory material is prepared by a method comprising the following steps:

[0116] mixing a granular material and a fine powder to obtain a mixed material, then, then subjecting the mixed material to hot-pressed sintering to obtain the refractory material.

[0117] The granular material refers to the part that cannot be sieved through a 180-mesh square hole sieve (Xinxiang Zhongtuo Machinery Equipment Co., Ltd.), that is, the part located on the 180-mesh square hole sieve. The particle size of the granular material is 0.088-10 mm, which is 0.088-10 mm, preferably 0.088-8 mm. For example, the particle size of the granular material can be 0.088 mm, 0.090 mm, 0.095 mm, 0.10 mm, 0.15 mm, 0.20 mm, 0.25 mm, 0.30 mm, 0.35 mm, 0.40 mm, 0.4 5 mm, 0.50 mm, 0.55 mm 0.60 mm, 0.65 mm, 0.70 mm, 0.75 mm, 0.80 mm, 0.85 mm, 0.90 mm, 0.95 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm or any range between them.

[0118] The fine powder refers to the part that passes through the 180-mesh square hole sieve, that is, the part located at the bottom of the 180-mesh square hole sieve, with a particle size?180 mesh, that is, a particle size?0.088 mm.

[0119] The hot-pressed sintering refers to a method of achieving sintering and preparation of materials under the combined action of applied pressure and temperature.

[0120] In a preferred embodiment of the present application, the mass ratio of the granular material to the fine powder is 30-65:35-70.

[0121] For example, the mass ratio of the granular material to the fine powder (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, 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 between them.

[0122] In a preferred embodiment of the present application, the granular material comprises corundum granular material and a mixed granular material, preferably, based on the mass percentage in the granular material, the corundum granular material is 65-100%, and the mixed granular material is 0-35%; [0123] preferably, the mixed granular material is selected from one or two or more selected from the group consisting of: CA6 granular material, C2M2A14 granular material, and CM2A8 granular material; [0124] preferably, the corundum granular material is one or two or more selected from the group consisting of: tabular corundum granular material, sintered corundum granular material, white corundum granular material, dense corundum granular material, and sub-white corundum granular material.

[0125] Based on the mass percentage in the granular material, the corundum granular material can be 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% or any range between them; and [0126] the mixed granular material can be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35% or any range between them.

[0127] The C2M2A14 granular material refers to 2CaO.Math.2MgO.Math.14Al.sub.2O.sub.3 granular material, while the CM2A8 granular material refers to CaO.Math.2MgO.Math.8Al.sub.2O.sub.3 granular material.

[0128] The tabular corundum granular material has a coarsely crystallized and well-developed a-Al.sub.2O.sub.3 crystal structure. The content of Al.sub.2O.sub.3 is above 97.0% with a tabular crystal structure. The tabular corundum granular material has small pores and more closed pores.

[0129] The sintered corundum granular material refers to a refractory clinker made from industrial alumina as raw material, finely ground into pellets or billets, and sintered at 1750-1900? C. It has a high bulk density, low porosity, and excellent resistance to thermal shock and slag erosion at high temperatures.

[0130] The white corundum granular material is an alumina raw material with an aluminum oxide (Al.sub.2O.sub.3) content of over 97.5%, which is prepared by electric melting using industrial alumina as the raw material. It contains a small amount of iron oxide, silicon oxide, and other components, and is white.

[0131] The sub white corundum granular material is produced using bauxite as raw material, and is called sub white corundum due to its chemical composition and physical properties being close to those of white corundum. This product has the hardness of white corundum and the toughness of brown corundum, making it an ideal advanced refractory material and grinding material.

[0132] In a preferred embodiment of the present application, the fine powder comprises Al.sub.2O.sub.3CaOMgO system fine powder and ZrO.sub.2-containing fine powder, preferably based on the mass percentage in the fine powder, the Al.sub.2O.sub.3CaOMgO system fine powder is 50-100%, and the ZrO.sub.2-containing fine powder is 0-50%; [0133] preferably, the Al.sub.2O.sub.3CaOMgO system fine powder comprises Al.sub.2O.sub.3-containing fine powder and one or two or more fine powders selected from CA6, C2M2A14, CM2A8, and MgOCaO system fine powders; [0134] preferably, the MgOCaO system fine powder is MgO-containing fine powder and/or CaO-containing fine powder; [0135] preferably, the Al.sub.2O.sub.3-containing fine powder is one or two or more selected from the group consisting of: the active ?-Al.sub.2O.sub.3 powder, ?-Al.sub.2O.sub.3 powder, ?-Al.sub.2O.sub.3 powder, aluminum hydroxide, industrial alumina, white corundum powder, sintered corundum powder, and tabular corundum powder; [0136] preferably, the MgO-containing fine powder is one or two or more selected from the group consisting of: magnesium carbonate, light-calcined magnesia, brucite, magnesium hydroxide, magnesium chloride, high-purity magnesia and fused magnesia; [0137] preferably, the CaO-containing fine powder is one or two or more selected from the group consisting of: quicklime, limestone, calcium hydroxide, CaO.Math.Al.sub.2O.sub.3, CaO.Math.Al.sub.2O.sub.3 (CA2), 12CaO.Math.7Al.sub.2O.sub.3 (C12A7), CA6, C2M2A14, and CM2A8; [0138] preferably, the ZrO.sub.2-containing fine powder is one or two or more selected from the group consisting of: monoclinic zirconia, tetragonal zirconia, desiliconized zirconium, and fused zirconia.

[0139] Considering that the phase of Al.sub.2O.sub.3CaOMgO fine powder after high-temperature hot-pressed sintering comprises corundum phase and one or two or more of CA6, CM2A8, and C2M2A14. Therefore, the phase of corundum can be transformed from Al.sub.2O.sub.3-containing fine powder at high temperature. CA6 can be obtained by reacting CA6 fine powder in CaO-containing raw materials and/or Al.sub.2O.sub.3-containing fine powder with CaO-containing raw materials such as quicklime, limestone, calcium hydroxide, CaO.Math.Al.sub.2O.sub.3, CaO.Math.2Al.sub.2O.sub.3, and 12CaO.Math.7Al.sub.2O.sub.3. C2M2A14 can be obtained by reacting C2M2A14 fine powder and/or Al.sub.2O.sub.3-containing fine powder, MgO-containing fine powder, and CaO-containing fine powder (except C2M2A14). CM2A8 can be obtained by reacting CM2A8 fine powder and/or Al.sub.2O.sub.3-containing fine powder, MgO-containing fine powder, and CaO-containing fine powder (except for CM2A8).

[0140] Based on the mass percentage in the fine powder, the Al.sub.2O.sub.3CaOMgO system fine powder can be, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% or any range between them; and the ZrO.sub.2-containing fine powder can be 0, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or any range between them.

[0141] The Al.sub.2O.sub.3-containing fine powder refers to a fine powder with the main chemical composition of Al.sub.2O.sub.3 or Al (OH).sub.3.

[0142] The MgO-containing fine powder refers to a fine powder with a main chemical composition of MgO or Mg (OH).sub.3.

[0143] The CaO-containing fine powder refers to a fine powder whose chemical composition comprises CaO components, or a fine powder containing CaO and Al.sub.2O.sub.3, or a fine powder containing CaO, MgO, and Al.sub.2O.sub.3.

[0144] The ZrO.sub.2-containing fine powder refers to the fine powder whose chemical composition is mainly ZrO.sub.2.

[0145] The active a-Al.sub.2O.sub.3 powder is an alumina powder with high activity (which is mainlya-Al.sub.2O.sub.3), obtained by processing industrial alumina or aluminum hydroxide as a raw material at 1250-1450? C.

[0146] The ?-Al.sub.2O.sub.3 powder is an alumina powder with a higher specific surface area and better adsorption properties, obtained by treating aluminum hydroxide as a raw material.

[0147] The ?-Al.sub.2O.sub.3 powder is an aluminum oxide powder with a certain hydration binding properties obtained by rapid high-temperature treatment at 600-900? C. using aluminum hydroxide as the raw material.

[0148] The main component of industrial alumina is a mineral whose main component is ?-Al.sub.2O.sub.3, which is prepared from aluminum hydroxide as raw material and calcined at 900-1250? C.

[0149] The white corundum powder is an aluminum oxide raw material prepared from industrial aluminum oxide as a raw material by electric melting, with a content of over 97.5% in Al.sub.2O.sub.3. It also comprises a small amount of iron oxide, silicon oxide, and other components, and is white in color.

[0150] The sintered corundum powder refers to a refractory clinker made from alumina as raw material, finely ground into pellets or billets, and sintered at 1750-1900? C. It has a high bulk density, low porosity, and excellent thermal shock resistance and slag erosion resistance at high temperatures.

[0151] The tabular corundum powder has a coarsely crystallized and well-developed a-Al.sub.2O.sub.3 crystal structure, with an Al.sub.2O.sub.3 content of over 97.0%. It has a tabular crystal structure with small pores and many closed pores.

[0152] The light-calcined magnesia is a magnesia raw material with high activity and magnesite phase, which is prepared by calcining magnesite (whose mainl component is magnesium carbonate) at 800-1000? C.

[0153] The brucite is a raw material with Mg (OH).sub.2 as the main component.

[0154] The sintered magnesia is a dense magnesia raw material with a MgO content of ? 94.5%, which is made from light-calcined magnesia and calcined at high temperature.

[0155] The fused magnesia is a dense magnesia material with MgO content ?96.5%, which is prepared from light-calcined magnesia or magnesite by arc melting.

[0156] The quicklime, also known as calcined lime, is mainly composed of calcium oxide. It is usually prepared by calcining natural rocks, which are mainly composed of calcium carbonate, at high temperatures to decompose and generate carbon dioxide and calcium oxide (chemical formula: CaO, also known as quicklime, or marble).

[0157] The monoclinic zirconia is a stable zirconia product at room temperature, and its crystal form is monoclinic.

[0158] The tetragonal zirconia is a stable zirconia in the form of a tetragonal phase.

[0159] The desilication zirconium is a zirconia prepared by removing SiO.sub.2 and other impurities from zircon sand.

[0160] The fused zirconia is a zirconia prepared by arc melting of zirconia powder

[0161] In a preferred embodiment of the present application, the hot-pressed sintering is performed by: [0162] putting the mixed into a mold of a high-temperature device for hot-pressed sintering, or molding the mixed material at normal temperature, and then putting it in a mold of a high-temperature device for hot-pressed sintering, or molding the mixed material at normal temperature, and pre-sintering it at a low-temperature, and then putting it into a mold of a high-temperature device for hot-pressed sintering.

[0163] For example, putting the mixed material into a mold of a high-temperature device for hot-pressed sintering means that the mixed material is put into the mold of the high-temperature device for heating up, and applying pressure when the temperature reaches the maximum temperature to achieve sintering, or continuously holding the temperature and pressure for a certain period of time to complete the hot-pressed sintering of the material, or putting the mixed material into a mold of a high-temperature device, applying the pressure when the temperature is raised to a certain temperature, then gradually increasing the temperature and simultaneously increasing the applied pressure until the temperature reaches the maximum temperature and the pressure reaches the maximum value, completing the hot-pressed sintering of the material, or continuously holding the temperature and pressure for a certain period of time to complete the hot-pressed sintering of the material: or putting the mixed material into a mold of a high-temperature device, gradually increasing the pressure applied to the mixed material while increasing the temperature until the temperature reaches the maximum temperature and the pressure reaches the maximum value, to complete the hot-pressed sintering of the material: or continuously holding the temperature and pressure for a certain period of time to complete the hot-pressed sintering of the material.

[0164] Molding the mixed at normal temperature and then putting it into a mold of a high-temperature device for hot-pressed sintering means that the mixed material is pressed into a billet at normal temperature, drying it, and then putting it in the mold of the high temperature device for hot-pressed sintering: or applying the pressure when the billet is heated to the maximum temperature to achieve sintering, or continuously holding the temperature and pressure for a certain period of time to complete hot-pressed sintering of the material: or putting the billet into a mold of a high-temperature device, applying the pressure when the temperature was raised to a certain temperature, then gradually increasing the temperature and simultaneously increasing the applied pressure until the temperature reaches the maximum temperature and the pressure reaches the maximum value to complete hot-pressed sintering of the material, or continuously holding the temperature and pressure for a certain period of time to complete the hot-pressed sintering of the material: or putting the billet into a mold of a high-temperature device and gradually increasing the pressure applied to the mixture while increasing the temperature until the temperature reaches the maximum temperature and the pressure reaches the maximum value to complete the hot-pressed sintering of the material, or continuously holding the insulation and pressure for a certain period of time to complete the hot-pressed sintering of the material.

[0165] The high-temperature device is a high-temperature device commonly used by those skilled in the art, such as a high-temperature furnace.

[0166] Molding the mixed material at normal temperature, and presintering it at low temperature, and then putting it into a mold of a high-temperature device for hot-pressed sintering means that the mixed material is pressed at normal temperature, and pre-sintered at 1350 to 1500? ? C. before hot-pressed sintering. The hot-pressed sintering operation is the same as above.

[0167] In a preferred embodiment of the present application, the temperature of hot-pressed sintering is 1550-1800? C., preferably the strength of the hot-pressed sintering is 0.5-30 MPa.

[0168] The strength of the hot-pressed sintering refers to the pressure value applied to a unit area of the sample.

[0169] For example, the temperature of hot-pressed sintering can be 1550? C., 1600? C., 1650? C., 1700? ? C., 1750? ? C., 1800? C. or any range between them.

[0170] For example, the strength of the hot-pressed sintering can be 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa, 6.5 MPa, 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa, 9 MPa, 9.5 MPa, 10 MPa, 10.5 MPa, 11 MPa, 11.5 MPa, 12 MPa, 12.5 MPa, 13 MPa, 13.5 MPa, 14 MPa, 14.5 MPa, 15 MPa, 20 MPa, 25 MPa, 30 MPa or any range between them.

[0171] The present application provides a preparation method for refractory materials, comprising the following steps: [0172] mixing a granular material and afine powder to obtain a mixed material, and the subjecting the mixed material to hot-pressed sintering to obtain the refractory material.

[0173] In a preferred embodiment of the present application, the mass ratio of the granular material to the fine powder is 30-65:35-70.

[0174] In a preferred embodiment of the present application, the particle size of the fine powder is ?0.088 mm; preferably, the particle size of the granular material is 0.088-10 mm, preferably 0.088-8 mm.

[0175] In a preferred embodiment of the present application, the hot-pressed sintering is performed by [0176] putting the mixed material into a mold of a high temperature device for hot-pressed sintering; or [0177] molding the mixed material at normal temperature, and then putting it into a mold of a high temperature device for hot-pressed sintering; or [0178] molding the mixed material at normal temperature, and presintering it at low temperature, and then putting it into a mold of a high temperature device for hot-pressed sintering.

[0179] The refractory material obtained by utilizing high temperature and high pressure to promote particle rearrangement and particle diffusion has low high-temperature liquid content, uniform organizational structure, and good thermal shock stability performance.

[0180] The present application provides a working lining of a ladle for molten steel smelting, which comprises the refractory material mentioned above or the refractory material prepared by the preparation method mentioned above.

[0181] The present application provides a working lining for molten aluminum smelting and transporting ladles, which comprises the refractory material or the refractory material prepared by the preparation method mentioned above.

[0182] The present application provides a refractory lining for an industrial furnaces, which comprises the refractory material or the refractory material prepared by the preparation method mentioned above.

EMBODIMENT

[0183] The present application provides a general and/or specific description of the materials and test methods used in the experiment. In the following examples, unless otherwise specified, % represents wt %, which is the mass percentage. The reagents or instruments used, if the manufacturer is not specified, are all conventional reagent products that can be obtained through market. Among them, Table 1 shows the sources of the raw materials used in the examples.

TABLE-US-00001 TABLE 1 Sources of raw materials used in the example Raw material Purity Producer Tabular corundum Al.sub.2O.sub.3 ? 97.0% Qingdao Anmai Aluminum powder Industry Co., Ltd CA6 fine powder Al.sub.2O.sub.3 90.5-92.5% Zibo Luzhong Refractory CaO 7.4-9.0% Materials Co., Ltd Sintered corundum Al.sub.2O.sub.3 ? 97.0% Jiangsu Jinghui Refractory granular material Materials Co., Ltd CA6 granular Al.sub.2O.sub.3 90.5-92.5% Zibo Luzhong Refractory material CaO 7.4-9.0% Materials Co., Ltd Light-calcined MgO ? 92.5% magnesium oxide CaOAl.sub.2O.sub.3 Al.sub.2O.sub.3 ? 64% Shandong Shengchuan CaO.sub.2 ? 35%% New Materials Co., Ltd ?-Al.sub.2O.sub.3 powder Al.sub.2O.sub.3 ? 96.0% Shandong Aluminum Corporation White corundum Al.sub.2O.sub.3 ? 97.5% Zhengzhou Yufa Group granular material ?-Al.sub.2O.sub.3 fine Al.sub.2O.sub.3 ? 93.5% Shandong Aluminum powder Corporation 12CaO7 Al.sub.2O.sub.3 Al.sub.2O.sub.3 ? 51% Shandong Shengchuan fine powder CaO ? 48%% New Materials Co., Ltd Industrial alumina Al.sub.2O.sub.3 ? 96.0% Shandong Aluminum fine powder Corporation Desilication ZrO.sub.2 + H.sub.2O ? 91% Shandong Golden Sun zirconium fine Zirconium Industry powder Co., Ltd Sub white Al.sub.2O.sub.3 ? 96.5% Luoyang Ruishi Company corundum granular material CM2A8 granular Al.sub.2O.sub.3 ? 84% Zibo Luzhong Refractory material CaO ? 5.0% Materials Co., Ltd MgO ? 8.0% Active ?-Al.sub.2O.sub.3 Al.sub.2O.sub.3 ? 97.0% Qingdao Anmai Aluminum fine powder Industry Co., Ltd Fused zirconia ZrO.sub.2 + H.sub.2O ? 98.5% Shandong Golden Sun fine powder Zirconium Industry Co., Ltd C2M2A14 Al.sub.2O.sub.3 ? 87% Zibo Luzhong Refractory granular CaO ? 6.2% Materials Co., Ltd material MgO ? 4.3% Tabular corundum Al.sub.2O.sub.3 ? 97.0% Qingdao Anmai Aluminum granular material Industry Co., Ltd White corundum Al.sub.2O.sub.3 ? 97.5% Zhengzhou Yufa Group fine powder High purity MgO ? 96.5% Yingkou Jiamagnesium magnesia powder Refractory Materials quick lime CaO ? 91.5% Co., Ltd Monoclinic ZrO.sub.2 + H.sub.2O ? 98.5% Shandong Golden Sun zirconia fine Haoye Co., Ltd powder Sub white Al.sub.2O.sub.3 ? 96.5% Luoyang Ruishi Co., Ltd corundum powder

Example 1

[0184] (1) 600 g of white corundum granular material, 40 g of active ?-Al.sub.2O.sub.3 fine powder, 100 g of industrial alumina fine powder, 60 g of CM2A8 fine powder, and 200 g of fused zirconia fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm;

[0185] (2) the mixed material was put in a mold of a high-temperature device for hot-pressed sintering, and applying pressure when the temperature was raised to a maximum temperature of 1640? C. When the maximum hot-pressed strength was 6 MPa, a corrosion-resistant refractory material was prepared.

[0186] The obtained refractory material was analyzed by powder XRD analysis, i.e. the obtained refractory material was ground to below 325 mesh, and then scanned by using an X-ray diffractometer (Bruker: D8 ADVANCE). The diffraction data were analyzed and matched with standard PDF cards to obtain the relevant phases. Then, the content of the relevant phases was obtained by fitting the diffraction data, and the main obtained phases are mainly corundum, CM2A8, and zirconia. Based on the mass percentage of the phase of the refractory material, the total content of corundum CM2A8 and zirconia was 99.1%, the corundum phase was 73.1%, the CM2A8 phase is 6.0%, and the zirconia phase was 20.0%.

[0187] The refractory material was analyzed by XRF according to standards, and measured according to GB/T21114-2007. Based on the mass percentage in the refractory material, the refractory material comprised 78.17% Al.sub.2O.sub.3, 0.43% MgO, 0.35% CaO, and 20.0% ZrO.sub.2.

[0188] The refractory material in this embodiment was measured according to GB/T2997-2000, and the bulk density was 3.30 g/cm.sup.3.

Example 2

[0189] (1) 300 g of dense corundum granular material, 200 g of tabular corundum particles, 140 g of CA6 fine powder, 92 g of industrial alumina fine powder, 15 g of CaCO.sub.3 fine powder, 160 g of white corundum powder, and 100 g of desiliconized zirconia fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm;

[0190] (2) the mixed material was put in a mold of a high-temperature device for hot-pressed sintering. When the temperature was raised to 1500? C., the pressure was applied. The temperature was increased while increasing the pressure. When the maximum temperature was raised to 1760? C., and the maximum hot-pressed strength was 2 MPa, a corrosion-resistant refractory material was prepared.

[0191] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum, CA6, and zirconia. Based on the mass percentage of the phase of the refractory material, the total content of corundum, CA6, and zirconia was 98.18%, the of corundum phase was 65.1%, the CA6 phase was 23.4%, and the zirconia phase are was 9.68%.

[0192] The analysis was carried out according to the same method as in Example 1, and the refractory material comprised 87.12% Al.sub.2O.sub.3, 1.93% CaO, and 9.65% ZrO.sub.2 based on the mass percentage of the refractory material.

[0193] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.12 g/cm.sup.3.

Example 3

[0194] (1) 260 g of sub white corundum granular material, 140 g of CM2A8 granular material, 60 g of white corundum powder, 100 g of CM2A8 powder, 17 g of C12A7 fine powder, 17.5 g of magnesium hydroxide powder, and 113 g of active ?-Al.sub.2O.sub.3 powder and 300 g of fused zirconia powder were stirred evenly to obtain a mixed material. The maximum particle size of the granular material is 8 mm:

[0195] (2) the mixed material was pressed, molding and drying, and then putting into a mold of a high-temperature device for hot-pressed sintering. When the maximum temperature was raised to 1780? C. and the maximum hot-pressed strength was 0.5 MPa, a corrosion-resistant refractory material was prepared.

[0196] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum, CM2A8, and zirconia. Based on the mass percentage of the phase of the refractory material, the total content of corundum, CM2A8, and zirconia was 98.5%, the corundum phase was 32.0%, the CM2A8 phase was 36.5%, and the zirconia phase was 30%.

[0197] The analysis was carried out according to the same method as in Example 1, the refractory material comprised 64.57% Al.sub.2O.sub.3, 2.94% MgO, 2.01% Ca0, and 30% ZrO.sub.2 based on the mass percentage of the refractory material.

[0198] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.30 g/cm.sup.3.

Example 4

[0199] (1) 300 g of sintered corundum granular material, 300 g dense of corundum granular material, 280 g of white corundum fine powder, 110 g of active ?-Al.sub.2O.sub.3 powder, and 13.5 g of calcium hydroxide fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm:

[0200] (2) the mixed material was put into a mold of a high-temperature device for hot-pressed sintering. The pressure was gradually applied when the temperature was raised to 1400? C. when the maximum temperature was raised to 1680? C. and the maximum hot-pressed strength was 1 MPa, a corrosion-resistant refractory material was prepared.

[0201] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 98.6%, the corundum phase was 88.0% and the CA6 phase was 10.6%.

[0202] The analysis was carried out according to the same method as in Example 1, and the refractory material comprised 98.99% Al.sub.2O.sub.3 and 0.89% CaO based on the mass percentage of the refractory material.

[0203] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 2.95 g/cm.sup.3.

Example 5

[0204] (1) 500 g of sub white corundum granular material, 73 g of CA6 fine powder, 100 g of white corundum powder, 28 g of ?-Al.sub.2O.sub.3 powder, and 40 g of CaO.Math.Al.sub.2O.sub.3 fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm:

[0205] (2) appropriate water was added into the mixed material, stirring evenly, casting, drying, pre-sintering at 1500? C. and putting into a mold of a high-temperature device for hot-pressed sintering. When the temperature was raised to 1770? C., the pressure was applied. When the maximum hot-pressed strength was 2 MPa, a corrosion-resistant refractory material was prepared.

[0206] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 96.9%, the corundum phase was 74.5% and the CA6 phase was 22.4%.

[0207] The analysis was carried out according to the same method as in Example 1, and the refractory material comprised 96.6% Al.sub.2O.sub.3 and 1.95% CaO based on the mass percentage of the refractory material.

[0208] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.12 g/cm.sup.3.

Example 6

[0209] (1) 650 g of tabular corundum granular material, 105 g of CA6 fine powder, 100 g of white corundum powder, and 223 g of aluminum hydroxide powder were stirred evenly to obtain a mixed material, and the maximum particle size of granular material is 5 mm:

[0210] (2) the mixed material was put into a mold of a high-temperature device for hot-pressed sintering, and the pressure was applied while increasing the temperature. When the maximum temperature was raised to 1700? C. and the maximum hot-pressed strength was 14 MPa, a corrosion-resistant refractory material was prepared.

[0211] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 98.1%, the corundum phase was 88.0% and the CA6 phase was 10.1%.

[0212] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 98.99% Al.sub.2O.sub.3 and 0.75% CaO.

[0213] The analysis was carried out according to the same method as in Example 1, and the bulk density was 3.28 g/cm.sup.3.

Example 7

[0214] (1) 500 g of sub white corundum granular material, 100 g of C2M2A14 fine powder, 45 g of CA2 fine powder, 7 g of fused magnesia powder, 89 g of ?-Al.sub.2O.sub.3 powder, and 260 g of white corundum powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material was 5 mm;

[0215] (2) appropriate water was added into the mixed material, stirring evenly, casting, drying, pre-sintering at 1350? C., and putting into a mold of a high-temperature device for hot-pressed sintering. When the temperature was raised to 1750? C., the pressure was applied. When the maximum hot-pressed strength was 1 MPa, a corrosion-resistant refractory material was prepared.

[0216] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and C2M2A14. Based on the mass percentage of the phase of the refractory material, the total content of corundum and C2M2A14 was 96.2%, the corundum phase was 75.0% and the C2M2A14 phase was 21.2%.

[0217] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 96.3% Al.sub.2O.sub.3, 1.0% MgO, and 1.20% CaO.

[0218] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.12 g/cm.sup.3.

Example 8

[0219] (1) 300 g of sub white corundum granular material, 90 g of CA6 fine powder, 17 g of calcium hydroxide fine powder, 138 g of active ?-Al.sub.2O.sub.3 powder, 265 g of ?-Al.sub.2O.sub.3 powder, and 460 g of white corundum powder were stirred evenly to obtain a mixed material. The maximum particle size of the granular material is 5 mm;

[0220] (2) the mixed material was pressed, molding, drying, treating at 1450? C. in a high-temperature device. The treated sample was put into a mold of a high-temperature device for hot-pressed sintering, and when the temperature rose to 1600? C., the pressure was applied. The pressure was increased while the temperature was increased. When the maximum temperature was raised to 1770? C. and the maximum hot-pressed strength was 3 MPa, a corrosion-resistant refractory material was prepared.

[0221] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 97.1%, the corundum phase was 74.7% and the CA6 phase was 22.4%.

[0222] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 96.4% Al.sub.2O.sub.3 and 1.91% CaO.

[0223] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.12 g/cm.sup.3.

Example 9

[0224] (1) 500 g of tabular corundum granular material, 100 g of CM2A8 fine powder, 11 g of calcium hydroxide fine powder, 17.5 g of high-purity magnesia powder, 122 g of industrial alumina fine powder, and 260 g of tabular corundum powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm:

[0225] (2) the mixed material was molded at normal temperature and dried, and then put into a mold of a high-temperature device for hot-pressed sintering. The pressure was applied when the temperature was raised to 1550? C., and the pressure was increased while increasing temperature. When the maximum temperature was raised to 1740? ? C., and the maximum hot-pressed strength was 4 MPa, a corrosion-resistant refractory material was prepared.

[0226] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CM2A8. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CM2A8 was 95.42%, The corundum phase was 73.1% and the phase was CM2A8.

[0227] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 95.7% Al.sub.2O.sub.3, 1.97% MgO, and 1.02% CaO.

[0228] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.12 g/cm.sup.3.

Example 10

[0229] (1) 260 g of sintered corundum granular material, 140 g of CA6 granular material, 120 g of sub white corundum fine powder, 55 g of Ca (OH).sub.2 fine powder, 200 g of tabular corundum powder, and 245 g of ?-Al.sub.2O.sub.3 fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 6 mm:

[0230] (2) the mixed material was pressed to mold at normal temperature, pre-sintering at 1500? C., and then putting into a mold of a high-temperature device. The pressure was applied while the temperature was raised. The maximum temperature was raised to 1750? C. and the maximum hot-pressed strength was 7 MPa, a corrosion-resistant refractory material was prepared.

[0231] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 98.8%, the corundum phase was 36.8% and the CA6 phase was 62.0%.

[0232] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 93.7% Al.sub.2O.sub.3 and 5.20% CaO.

[0233] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.25 g/cm.sup.3.

Example 11

[0234] (1) 195 g of tabular corundum granular material, 105 g of CM2A8 granular material, 70 g of active ?-Al.sub.2O.sub.3 powder, 280 g of CM2A8 fine powder, 100 g of tetragonal zirconia fine powder, and 250 g of fused zirconia fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm;

[0235] (2) the mixed material was molded at normal temperature, and then put into a mold of a high-temperature device for hot-pressed sintering. The pressure was applied while the temperature was raised. When the maximum temperature was raised to 1550? C. and the maximum hot-pressed strength was 30 MPa, a corrosion-resistant refractory material was prepared.

[0236] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum, CM2A8, and zirconia. Based on the mass percentage of the phase of the refractory material, the total content of corundum, CM2A8, and zirconia was 99.6%, the corundum phase was 26.5%, the CM2A8 phase was 38.1%, and the zirconia phase was 35%.

[0237] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 59.5% Al.sub.2O.sub.3, 3.01% MgO, 2.03% CaO, and 35% ZrO.sub.2.

[0238] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.45 g/cm.sup.3.

Example 12

[0239] (1) 350 g of sub white corundum granular material, 300 g of sintered corundum granular material, 175 g of monoclinic zirconia fine powder, 52.5 g of CM2A8 fine powder, and 188 g of aluminum hydroxide powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 3 mm; (2) the mixed material was put into a mold of a high-temperature furnace device for hot-pressed sintering. When the temperature was raised to 1350? C., the pressure was applied, and the pressure was increased while increasing the temperature. When the maximum temperature was raised to 1600? ? C., and the maximum hot-pressed strength was 15 MPa, a corrosion-resistant refractory material was prepared.

[0240] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum, CM2A8, and zirconia. Based on the mass percentage of the phase of the refractory material, the total content of corundum, CA6, and zirconia was 97.15%, the corundum phase was 75.4%, the CM2A8 phase was 5.25%, and the zirconia phase was 16.5%.

[0241] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 80.8% Al.sub.2O.sub.3, 0.30% CaO, 0.43% MgO, and 16.9% ZrO.sub.2.

[0242] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.26 g/cm.sup.3.

Example 13

[0243] (1) 195 g of sintered corundum granular material, 105 g of CA6 granular material, 100 g of industrial alumina fine powder, 138.5 g of ?-Al.sub.2O.sub.3 powder, 460 g of CA6 fine powder, and 11.5 g of calcium hydroxide powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 8 mm;

[0244] (2) the mixed material was molded at normal temperature, drying, treating at 1500? C., and then putting into a mold of a high-temperature furnace for hot-pressed sintering. When the maximum temperature was raised to 1700? ? C., and the maximum hot-pressed strength was 21 MPa, a corrosion-resistant refractory material was prepared.

[0245] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 97.7%, the corundum phase was 31.2% and the CA6 was 66.5%.

[0246] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 93.1% Al.sub.2O.sub.3 and 5.58% CaO.

[0247] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.25 g/cm.sup.3

Example 14

[0248] (1) 300 g of sintered corundum granular material, 460 g of industrial alumina fine powder, 140 g of CA6 fine powder, 11.5 g of calcium hydroxide powder, and 93 g of YAl.sub.2O.sub.3 powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm:

[0249] (2) the mixed material was put into a mold of a high-temperature device for hot-pressed sintering. When the maximum temperature was raised to 1650? C. and the maximum hot-pressed strength was 8 MPa, a corrosion-resistant refractory material was prepared.

[0250] The analysis was carried out according to the same method as in Example 1, and the phases were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 95.4%, The corundum phase was 75.1% and the CA6 phase was 20.3%.

[0251] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 96.1% Al.sub.2O.sub.3 and 1.94% CaO.

[0252] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 2.90 g/cm.sup.3.

Example 15

[0253] (1) 260 g of sintered corundum granular material, 140 g of CM2A8 granular material, 40 g of industrial alumina fine powder, 83 g of ?-Al.sub.2O.sub.3 powder, and 480 g of CM2A8 fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 10 mm:

[0254] (2) the mixed material was put into a mold of a high-temperature device for hot-pressed sintering. When the maximum temperature was raised to 1650? C. and the maximum hot-pressed strength was 4 MPa, a corrosion-resistant refractory material was prepared.

[0255] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CM2A8. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CM2A8 was 98.8%, the corundum phase was 36.8% and the CM2A8 was 62%.

[0256] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 90.1% Al.sub.2O.sub.3, 5.20% MgO, and 3.60% CaO.

[0257] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 2.90 g/cm.sup.3.

Example 16

[0258] (1) 195 g of sintered corundum granular material, 105 g of CM2A8 granular material, 100 g of industrial alumina fine powder, 40 g p Al.sub.2O.sub.3 fine powder, and 560 g of CM2A8 fine powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 1 mm:

[0259] (2) the mixed material was put into a mold of a high-temperature device for direct hot-pressed sintering. When the maximum temperature was 1800? C. and the hot-pressed strength was 2 MPa, a corrosion-resistant refractory material was prepared.

[0260] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CM2A8. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CM2A8 was 98.3%, the corundum phase was 31.8% and the CM2A8 phase was 66.5%.

[0261] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 89.3% Al.sub.2O.sub.3, 5.58% MgO, and 3.88% CaO.

[0262] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.65 g/cm.sup.3.

Example 17

[0263] (1) 300 g of sintered corundum granular material, 585 g of industrial alumina fine powder, 40 g of ?-Al.sub.2O.sub.3 powder, 45 g of calcium hydroxide fine powder, and 48 g of fused magnesia powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 1 mm;

[0264] (2) the mixed material is molded at normal temperature and dried, treated at 1450? C., and then put into a mold of a high-temperature device for hot-pressed sintering. When the maximum temperature was 1720? C., and the hot-pressed strength was 3 MPa, a corrosion-resistant refractory material was prepared.

[0265] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum, CM2A8, and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CM2A8 was 90.0%, the corundum phase was 44.0%, the CM2A8 phase was 22.6%, and the CA6 phase was 23.4%.

[0266] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 90.8% Al.sub.2O.sub.3, 4.28% MgO, and 3.13% CaO.

[0267] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 2.93 g/cm.sup.3.

Example 18

[0268] (1) 650 g of white corundum granular material, 105 g of CA6 fine powder, and 250 g of white corundum powder were stirred evenly to obtain a mixed material, and the maximum particle size of the granular material is 5 mm:

[0269] (2) the mixed material was put into a mold of a high-temperature device for hot-pressed sintering, and the pressure was increased while increasing the temperature.

[0270] When the maximum temperature was raised to 1715? C. and the maximum hot-pressed strength was 7.5 MPa, a corrosion-resistant refractory material was prepared.

[0271] The analysis was carried out according to the same method as in Example 1, and the phases obtained were mainly corundum and CA6. Based on the mass percentage of the phase of the refractory material, the total content of corundum and CA6 was 99.53%, the corundum phase was 89.50% and the CA6 phase was 10.3%.

[0272] The analysis was carried out according to the same method as in Example 1, and based on the mass percentage in the refractory material, the obtained refractory material comprised 98.99% Al.sub.2O.sub.3 and 0.84% CaO.

[0273] The analysis was carried out according to the same method as in Example 1, and the bulk density obtained was 3.25 g/cm.sup.3.

Comparative Example 1

[0274] The difference between Comparative Example 1 and Example 1 was that Comparative Example 1 used a conventional preparation method, that is, the method of Example 1 in China patent application CN107500747A was used to obtain a refractory material.

[0275] The analysis was carried out according to the same method as in Example 1, and the chemical composition of the obtained refractory material comprised Al.sub.2O.sub.3 92.11% and CaO 7.02%, based on the mass percentage in the refractory material.

[0276] The analysis was carried out according to the same method as in Example 1, and the phases in Comparative Example 1 were mainly CA6, corundum, CaO.Math.Al.sub.2O.sub.3, and CaO.Math.2Al.sub.2O.sub.3. Based on the mass percentage of the phases in the refractory material, the CA6 phase was 69.1%, the corundum phase was 24.2%, the CaO.Math.Al.sub.2O.sub.3 phase was 2.30%, and the CaO.Math.2Al.sub.2O.sub.3 phase was 2.31%.

[0277] The analysis was carried out according to the same method as in Example 1, and the bulk density of the refractory material in Comparative Example 1 was 3.05 g/cm.sup.3.

TABLE-US-00002 TABLE 2 Table of Raw Materials Used in Examples and Comparative Examples and the Refractory Materials Obtained The ratio of granular Chemical material Phase composition Bulk to fine composition and density powder and content (%) content (%) (g/cm) Example 1 60:40 CM2A8: 6.0 78.17% Al.sub.2O.sub.3 3.30 corundum: 73.1 0.35% CaO zirconia: 20.0 0.43% MgO 20.0% ZrO.sub.2 Example 2 50:50 CA6: 23.4 87.12% Al.sub.2O.sub.3 3.12 corundum: 65.1 1.93% CaO zirconia: 9.68 9.65% ZrO.sub.2 Example 3 40:60 corundum: 32.0 64.57% Al.sub.2O.sub.3 3.30 CM2A8: 36.5 2.01% CaO zirconia: 30.0 2.94% MgO 30% ZrO.sub.2 Example 4 60:40 CA6: 10.6 98.99% Al.sub.2O.sub.3 2.95 corundum: 88.0 0.89% CaO Example 5 50:50 CA6: 22.4 96.6% Al.sub.2O.sub.3 3.12 corundum: 74.5 1.95% CaO Example 6 65:35 corundum: 88 98.99% Al.sub.2O.sub.3 3.28 CA6: 10.1 0.75% CaO Example 7 50:50 C2M2A14: 21.2 96.3% Al.sub.2O.sub.3 3.12 corundum: 75.0 1.20% CaO 1.0% MgO Example 8 30:70 CA6: 22.4 96.4% Al.sub.2O.sub.3 3.12 corundum: 74.7 1.91% CaO Example 9 50:50 corundum: 73.1 95.7% Al.sub.2O.sub.3; 3.12 CM2A8: 22.32 1.02% CaO 1.97% MgO Example 10 40:60 CA6: 62.0 93.7% Al.sub.2O.sub.3; 3.25 corundum: 36.8 5.20% CaO Example 11 30:70 Corundum: 26.5 59.5% Al.sub.2O.sub.3; 3.45 CM2A8: 38.1 3.01% MgO zirconia: 35 2.03% CaO 35% ZrO.sub.2 Example 12 65:35 CM2A8: 5.25 80.8% Al.sub.2O.sub.3 3.26 corundum: 75.4 0.43% MgO zirconia: 16.5 0.30% CaO 16.9% ZrO.sub.2 Example 13 30:70 corundum: 31.2 93.1% Al.sub.2O.sub.3 3.25 CA6: 66.5 5.58% CaO Example 14 30:70 corundum: 75.1 96.1% Al.sub.2O.sub.3; 2.90 CA6: 20.3 1.94% CaO Example 15 40:60 corundum: 36.8 90.1% Al.sub.2O.sub.3 2.90 CM2A8: 62.0 3.60% CaO 5.20% MgO Example 16 30:70 corundum: 31.8 89.3% Al.sub.2O.sub.3 3.65 CM2A8: 66.5 3.88% CaO 5.58% MgO Example 17 30:70 corundum: 44.0 90.8% Al.sub.2O.sub.3 2.93 CM2A8: 22.6 3.13% CaO CA6: 23.4 4.28% MgO Example 18 65:35 corundum: 89.50 98.99% Al.sub.2O.sub.3 3.25 CA6: 10.3 0.84% CaO Comparative 65:35 corundum: 24.2 92.11% Al.sub.2O.sub.3 3.05 Example 1 CA6: 69.1 7.02% CaO CaOAl.sub.2O.sub.3: 2.3 CaO2Al.sub.2O.sub.3: 2.31

Experiment Example 1: Dynamic Slag Erosion Experiment

[0278] The dynamic slag erosion experiment was conducted by comparing the refractory material obtained from Example 1 with the refractory material sample obtained from Comparative Example 1.

[0279] The sample for dynamic slag penetration requires a longer length to be fixed on the rotating axis. Given the high bulk density, high content of corundum phase, and high hardness of the refractory material obtained in Example 1, it is difficult to drill into a ?15 mm cylindrical sample and only cut into square strips. As a measurement of erosion rate, the size of the opposite side shall prevail, so that cutting the sample into square strips does not affect the accuracy of the final result. As a comparison, the castable of Comparative Example 1 was poured into sample of the same size.

[0280] The dynamic slag erosion experiment has the following conditions: the deoxygenation method adopts metal aluminum deoxygenation, with an experimental temperature of 1600? C. and a hydrogen atmosphere: the slag system adopts CaOAl.sub.2O.sub.3SiO.sub.2 system, and the steel slag composition is 51% CaO, 30% Al.sub.2O.sub.3, 11% SiO.sub.2, 8% MgO, and CaO/SiO.sub.2 is 4.6.

[0281] The castable of Comparative Example 1 and the refractory material described in Example 1 were respectively bonded to the above motor using high-temperature adhesive, and the rotation speed was controlled at 10 cycles/minute. The experimental results are shown in FIG. 1A and FIG. 1B, respectively.

[0282] It can be seen from FIG. 1A and FIG. 1B that after rotating for 8 minutes, the castable sample of Comparative Example 1 immersed in steel slag has been collapsed. However, the refractory material in Example 1 has not changed much, and the roundness is still very obvious, basically without much change. The width of the unreacted interface was measured by using a vernier caliper after cutting open the sample, which showed that it was damaged by 0.2-0.5 mm, indicating that the corrosion resistance of the refractory material obtained from Example 1 is very excellent.

Experiment Example 2: Static Slag Erosion Experiment

[0283] The static slag erosion experiment adopts the crucible method. Wherein FIG. 2A is a schematic diagram of the static crucible method for molten steel smelting.

[0284] The sample in Example 1 was first hot-pressed into a ?45 mm sample, and then drilled out a ?30 mm?40 mm pit. The castable of Comparative Example 1 was also poured into a ?45 mm sample, with an internal pit size of ?30 mm?40 mm. The experimental conditions are 1600? C., argon gas atmosphere, and deoxygenation using metal aluminum. The slag system adopts CaOAl.sub.2O.sub.3SiO.sub.2 system, and the steel slag composition is 51% CaO, 30% Al.sub.2O.sub.3, 11% SiO.sub.2, 8% MgO, and CaO/SiO.sub.2 is 4.6. The static slag erosion results are shown in FIG. 2B, wherein a, b, and c represent the contour structures of the castable in Comparative Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively, and d, e, and f represent the contour structures of the sample in Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively.

[0285] From FIG. 2B, it can be seen that for the castable in Comparative Example 1, some parts have already been completely penetrated and eroded by slag at 40 minutes, and the sample has been collapsed. Although the erosion thickness of some part is shown to be 270 ?m, the slag has fully penetrated, which is caused by the structure and performance of traditional refractory materials. Due to the uneven structure of traditional materials, they are often good as a whole, but some parts are unbearable. The sample in Example 1 of the present application exhibits excellent uniformity and a very complete structure.

[0286] In addition, FIG. 2C shows a comparison of the microstructure between the castable in Comparative Example 1 and the sample in Example 1 of this application, a. b and c represent the microstructure of castable in Comparative Example at 30 minutes, 40 minutes, and 50 minutes, respectively, and d. e and f represent the microstructure of the sample in Example 1 at 30 minutes, 40 minutes, and 50 minutes, respectively. From the microstructure, it can also be seen that the structure of the castable in Comparative Example 1 is very uneven, and the slag can penetrate deeply along the areas with more pores. However, the metamorphic layer in Example 1 of this application is very thin and uniform. This also demonstrates that the performance of the sample of the present application is excellent.

Experiment Example 3: Experiment on Slag Erosion and Thermal Shock Stability

[0287] The experiments were conducted on slag erosion and thermal shock stability of the refractory material obtained from Examples 1-17 and Comparative Example 1. Wherein the measurements regarding slag erosion are as follows: firstly, the crucible after the experiment is cut along the middle surface, and samples are taken on the crucible wall for electron microscopy observation and measurement, in order to measure the slag erosion. In addition, the thermal shock stability experiment is determined in accordance with GB/T 30873-2014, and the results are shown in Table 3.

TABLE-US-00003 TABLE 3 Experimental Data Slag erosion, Thermal shock ?m/40 min stability, times 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 7.5 mm 15 Example 1

[0288] The application and performance evaluation of refractory materials are not only related to their resistance to slag erosion, but also need to consider the thermal shock stability of refractory materials under temperature rapid cooling and rapid heating conditions. If the thermal shock stability is not good, cracks may appear during use, affecting the material's performance.

[0289] For erosion resistance, the addition of ZrO.sub.2 is advantageous at the same bulk density. Compared with CA6, C2M2A8, and CM2A8, corundum has better erosion resistance. For the same composition, refractory materials with high bulk density have better erosion resistance.

[0290] The addition of ZrO.sub.2 is advantageous for thermal shock stability. The addition of CA6 has better thermal shock stability than that of the refractory materials with the same quality of corundum, C2M2A8, and CM2A8. For the same composition, if the volume density is small, the thermal shock stability is relatively better.

[0291] In addition, it is also necessary to consider the cost-performance ratio of refractory materials. For example, refractory materials added with zirconia have good slag erosion resistance and thermal shock stability, and the performance is also excellent when the addition is in large amounts, but zirconia is relatively expensive. Therefore, for the embodiments of the present application, the performance advantages and disadvantages are the result of comprehensive comparison.

[0292] The above is only a preferred embodiment of the present application and is not intended to limit the present application in other forms. Any person familiar with this field may make use of the disclosed technical content to change or adapt it to embodiments with equivalent variations. However, any simple modifications, equivalent variations, or adaptations of the above embodiments based on the technical essence of the present application, without departing from the content of the technical solution of the present application, still fall within the scope of protection of the technical solution of the present application.