CN117209266B - Preparation method of high thermal shock magnesia-alumina spinel refractory material with flaky crystals at grain boundaries - Google Patents
Preparation method of high thermal shock magnesia-alumina spinel refractory material with flaky crystals at grain boundaries Download PDFInfo
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- CN117209266B CN117209266B CN202311181897.8A CN202311181897A CN117209266B CN 117209266 B CN117209266 B CN 117209266B CN 202311181897 A CN202311181897 A CN 202311181897A CN 117209266 B CN117209266 B CN 117209266B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 62
- 239000011029 spinel Substances 0.000 title claims abstract description 62
- 230000035939 shock Effects 0.000 title claims abstract description 34
- 239000013078 crystal Substances 0.000 title claims abstract description 29
- 239000011819 refractory material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000007767 bonding agent Substances 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 21
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 238000005272 metallurgy Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011468 face brick Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a preparation method of a high thermal shock magnesia-alumina spinel refractory material with flaky crystals at grain boundaries. The preparation method of the high thermal shock magnesia-alumina spinel refractory material with flaky crystals at the grain boundaries takes sintered magnesia-alumina spinel particles, magnesia-alumina spinel fine powder, alumina micropowder and sodium-containing additive as raw materials, and the raw materials are subjected to blank making and molding; drying the blank, and sintering in a high-temperature kiln or an electric furnace at a maximum sintering temperature of 1650-1700 ℃; the sodium-containing additive and the impurity phase at the grain boundary form a liquid phase to dissolve the magnesia-alumina spinel and slowly crystallize, and flaky NMA grows at the grain boundary to separate the grain boundary through epitaxial growth at the grain boundary. The invention greatly improves the thermal shock stability of the magnesia-alumina spinel material, and can be applied to environments with high requirements on the thermal shock stability, such as hydrogen metallurgy, alkali-containing waste liquid incinerators and the like.
Description
Technical Field
The invention belongs to the field of refractory materials, and particularly relates to a preparation method of a high-thermal-shock magnesia-alumina spinel refractory material with flaky crystals at grain boundaries.
Background
Because of the great emission reduction potential, hydrogen metallurgy has become a necessary high point for tap steel enterprises, and a plurality of iron and steel companies at home and abroad are greatly distributing projects such as hydrogen energy metallurgy, green hydrogen preparation, hydrogen energy supply and the like. From "carbon metallurgy" to "hydrogen metallurgy", the iron and steel industry is expected to remove caps with high carbon emissions, high pollution and high energy consumption.
The hydrogen-based direct reduction iron-making shaft furnace is characterized in that a mixed gas of hydrogen and carbon monoxide is used as a reducing agent to convert iron ore into direct reduced iron, and the direct reduced iron is put into an electric furnace for further smelting. The addition of hydrogen as a reducing agent effectively controls the carbon emission; compared with a hydrogen-rich reduction blast furnace, the discharge amount of carbon dioxide per ton can be reduced by more than 50 percent; this approach is more suitable for hydrogen metallurgy; the blast furnace has the hydrogen-rich and carbon-reducing amplitude of 10-20% and limited effect; the gas-based direct reduction shaft furnace process is a direct reduction technology, does not need links such as coking, sintering, iron making and the like, can control carbon emission from the source, has a carbon reduction range of more than 50% compared with the hydrogen-rich reduction of a blast furnace, has larger emission reduction potential, and is an effective way for rapidly expanding the production of direct reduced iron; however, the gas-based shaft furnace has the problems of strong heat absorption effect, increased amount of H 2 fed into the furnace, increased production cost, reduced reduction rate, high product activity, difficult passivation and transportation and the like; the method has obvious carbon reduction effect in a hydrogen metallurgy mode no matter the blast furnace ironmaking or the gas-based shaft furnace direct reduction of iron.
Because the operating temperature of hydrogen metallurgy is higher, the reducibility is stronger than that of a high-temperature gas pipeline required by mixed gas and the chemical stability of refractory materials in a furnace entering area is good (low iron and little silicon), and a reaction product contains a large amount of water vapor and needs refractory materials without hydratable phases.
The existing hot face bricks of the hydrogen-based direct reduction iron-smelting shaft furnace adopt 60-70 mullite bricks, and SiO 2 + H2 = SiO(g)↑ + H2 O reaction can be generated due to the fact that a large amount of silicon dioxide is contained, so that the problems of weight loss and strength attenuation can be caused under long-term use, and the use stability and safety of a furnace lining, particularly an airway supporting brick, are greatly influenced.
The aluminum-rich magnesia-alumina spinel material has no material weight loss and hydration problems in the hydrogen atmosphere, and the material strength cannot be attenuated, but the thermal shock stability is inferior to that of 60-70 mullite bricks due to the fact that the expansion coefficient of the material is higher than that of mullite.
In order to better meet the practical use conditions, the invention controls the epitaxial growth at the grain boundary by introducing the sodium-containing additive, and flaky NMA grows at the grain boundary to separate the grain boundary. In the thermal shock process, the lamellar crystal at the grain boundary can play roles in crack deflection and pinning, so that the thermal shock stability of the magnesia-alumina spinel material is greatly improved, and the lamellar crystal can be applied to environments with high requirements on the thermal shock stability, such as hydrogen metallurgy, alkali-containing waste liquid incinerators and the like.
Disclosure of Invention
In order to solve the problems of insufficient use stability and safety of the existing refractory materials in environments with high requirements on thermal shock stability, such as hydrogen metallurgy, alkali-containing waste liquid incinerators and the like, the invention aims to provide a preparation method of a high-thermal shock magnesia-alumina spinel refractory material with flaky crystals at grain boundaries.
The invention adopts the following technical scheme for accomplishing the purposes:
a preparation method of a high thermal shock magnesia-alumina spinel refractory material with flaky crystals at grain boundaries comprises the following raw materials in percentage by mass:
15 to 45 percent of 3 to 1mm sintered magnesia alumina spinel particles,
10 To 45 percent of 1 to 0.088mm sintered magnesia-alumina spinel particles,
20 To 45 percent of 325 mesh sintered magnesia-alumina spinel fine powder,
5-10% Of alumina micropowder,
Adding sodium-containing additive 0.2-0.6%,
Adding 3-5% of temporary bonding agent;
Sintering magnesia-alumina spinel particles, magnesia-alumina spinel fine powder, alumina micropowder and sodium-containing additive as raw materials, and performing blank making and molding; drying the blank, and sintering in a high-temperature kiln or an electric furnace at a maximum sintering temperature of 1650-1700 ℃; the sodium-containing additive and the impurity phase at the grain boundary form a liquid phase to dissolve the magnesia-alumina spinel and slowly crystallize, and flaky NMA grows at the grain boundary to separate the grain boundary through epitaxial growth at the grain boundary.
The aluminum content in the sintered magnesia-alumina spinel is 75% -78%.
The sodium-containing additive is one or more of NaCO 3、NaHCO3, naCl and NaF. The precipitated flaky crystal is Mg-beta' -Al 2O3, which is limited by a growth space and is positioned at the grain boundary.
Compared with the prior art, the preparation method of the high thermal shock magnesia-alumina spinel refractory material with flaky crystals at the grain boundaries has the advantages that the magnesia-alumina spinel material rich in aluminum has no problems of material weight loss and hydration in the hydrogen atmosphere, and the material strength cannot be attenuated; sodium-containing additives are introduced and lamellar crystals are grown at the grain boundaries to separate the grain boundaries by epitaxial growth at the grain boundaries. In the thermal shock process, the lamellar crystal at the grain boundary can play roles in crack deflection and pinning, so that the thermal shock stability of the magnesia-alumina spinel material is greatly improved, and the lamellar crystal can be applied to environments with high requirements on the thermal shock stability, such as hydrogen metallurgy, alkali-containing waste liquid incinerators and the like.
Drawings
FIG. 1 is a microstructure (2000 x magnification) of an aggregate portion of a high thermal shock magnesia-alumina spinel refractory with flaky crystals at grain boundaries prepared in example one;
FIG. 2 is a microstructure (magnification: 5000 times) of a matrix portion of a high thermal shock magnesia-alumina spinel refractory with flaky crystals at grain boundaries, which was prepared in example one.
Detailed Description
The present invention will now be described by way of example for the purpose of fully illustrating the features of the present invention, but the embodiments of the present invention are not limited to the following examples, and may be appropriately modified within the allowable range according to the actual circumstances:
the invention will be described with reference to specific examples:
Examples
The ingredients of each component are as follows: 30% of 3-1mm sintered magnesia-alumina spinel particles, 35% of 1-0.088mm sintered magnesia-alumina spinel particles, 30% of 325-mesh sintered magnesia-alumina spinel fine powder, 5% of alumina micro powder, 0.5% of NaCl and 4% of temporary bonding agent. Adding the sodium-containing additive into the temporary bonding agent, uniformly stirring, adding into the uniformly mixed aggregate, uniformly stirring, adding the premixed fine powder part, mixing by an edge mill, and performing machine pressing molding after ageing; and drying the blank, and sintering at 1650 ℃.
The high thermal shock magnesia-alumina spinel refractory material with flaky crystals at the grain boundary is prepared. The normal temperature compressive strength is 106MPa. According to DIN 51068:2008 standard, the number of times of water-cooling thermal shock at 950 ℃ can reach more than 30 times.
In the first example, the aggregate was AR78 spinel, and it was found that some grain boundaries were grown to give flaky crystals, and the energy spectrum of flaky crystals grown at the grain boundaries showed Na 2 O (1.7%), mgO (14.9%), al2O3 (82.2%), and CaO (1.2%).
The second view is a matrix part of the first embodiment, and it can be seen that flaky crystals grow at grain boundaries, and the energy spectrum shows Na 2O（2.5%-6.7%）、MgO（3.7%-8.5%）、Al2O3 (88.4% -90.8%) and CaO (1.1% -1.6%).
The ingredients of each component are as follows: 30% of 3-1mm sintered magnesia-alumina spinel particles, 35% of 1-0.088mm sintered magnesia-alumina spinel particles, 30% of 325 mesh sintered magnesia-alumina spinel fine powder, 5% of alumina micro powder and 4% of an additional temporary bonding agent; adding the binding agent into the uniformly mixed aggregate, uniformly stirring, adding the premixed fine powder part, mixing by an edge mill, and performing machine pressing molding after ageing. And drying the blank, and sintering at 1650 ℃.
The conventional magnesia-alumina spinel refractory material is prepared. The normal temperature compressive strength is 122MPa. The number of water-cooling thermal shock at 950 ℃ is 11 according to DIN 51068:2008 standard.
Examples
The ingredients of each component are as follows: 45% of 3-1mm sintered magnesia-alumina spinel particles, 25% of 1-0.088mm sintered magnesia-alumina spinel particles, 20% of 325 mesh sintered magnesia-alumina spinel fine powder, 10% of alumina micro powder, 0.2% of NaF and 3% of temporary bonding agent. Adding the sodium-containing additive into the temporary bonding agent, uniformly stirring, adding into the uniformly mixed aggregate, uniformly stirring, adding the premixed fine powder part, mixing by an edge mill, and performing machine pressing molding after ageing. The green body is dried and then burned at 1700 ℃.
The high thermal shock magnesia-alumina spinel refractory material with flaky crystals at the grain boundary is prepared. The normal temperature compressive strength is 118MPa. According to DIN 51068:2008 standard, the number of times of water-cooling thermal shock at 950 ℃ can reach more than 30 times.
Examples
The ingredients of each component are as follows: 20% of 3-1mm sintered magnesia-alumina spinel particles, 40% of 1-0.088mm sintered magnesia-alumina spinel particles, 30% of 325 mesh sintered magnesia-alumina spinel fine powder, 10% of alumina micro powder, 0.6% of NaHCO 3 and 5% of temporary bonding agent. Adding the sodium-containing additive into the temporary bonding agent, uniformly stirring, adding into the uniformly mixed aggregate, uniformly stirring, adding the premixed fine powder part, mixing by an edge mill, and performing machine pressing molding after ageing. The green body is dried and then burned at 1680 ℃.
The high thermal shock magnesia-alumina spinel refractory material with flaky crystals at the grain boundary is prepared. The normal temperature compressive strength is 109MPa. According to DIN 51068:2008 standard, the number of times of water-cooling thermal shock at 950 ℃ can reach more than 30 times.
Examples
The ingredients of each component are as follows: 30% of 3-1mm sintered magnesia-alumina spinel particles, 15% of 1-0.088mm sintered magnesia-alumina spinel particles, 45% of 325 mesh sintered magnesia-alumina spinel fine powder, 10% of alumina micro powder, 0.2% of Na 2CO3% of temporary bonding agent and 5% of temporary bonding agent. Adding the sodium-containing additive into the temporary bonding agent, uniformly stirring, adding into the uniformly mixed aggregate, uniformly stirring, adding the premixed fine powder part, mixing by an edge mill, and performing machine pressing molding after ageing. Drying the blank, and sintering at 1660 ℃.
The high thermal shock magnesia-alumina spinel refractory material with flaky crystals at the grain boundary is prepared. The normal temperature compressive strength is 112MPa. According to DIN 51068:2008 standard, the number of times of water-cooling thermal shock at 950 ℃ can reach more than 30 times.
Examples
The ingredients of each component are as follows: 15% of 3-1mm sintered magnesia-alumina spinel particles, 45% of 1-0.088mm sintered magnesia-alumina spinel particles, 30% of 325 mesh sintered magnesia-alumina spinel fine powder, 10% of alumina micro powder, 0.3% of NaCl and 0.3% of NaF, and 4% of temporary bonding agent. Adding the sodium-containing additive into the temporary bonding agent, uniformly stirring, adding into the uniformly mixed aggregate, uniformly stirring, adding the premixed fine powder part, mixing by an edge mill, and performing machine pressing molding after ageing. And drying the blank, and sintering at 1690 ℃.
The high thermal shock magnesia-alumina spinel refractory material with flaky crystals at the grain boundary is prepared. The normal temperature compressive strength is 123MPa. According to DIN 51068:2008 standard, the number of times of water-cooling thermal shock at 950 ℃ can reach more than 30 times.
Claims (4)
1. A preparation method of a high thermal shock magnesia-alumina spinel refractory material with flaky crystals at grain boundaries is characterized by comprising the following steps: the Gao Rezhen magnesia alumina spinel refractory material comprises the following raw materials in percentage by mass:
15 to 45 percent of 3 to 1mm sintered magnesia alumina spinel particles,
10 To 45 percent of 1 to 0.088mm sintered magnesia-alumina spinel particles,
20 To 45 percent of 325 mesh sintered magnesia-alumina spinel fine powder,
5-10% Of alumina micropowder,
Adding sodium-containing additive 0.2-0.6%,
Adding 3-5% of temporary bonding agent;
Sintering magnesia-alumina spinel particles, magnesia-alumina spinel fine powder, alumina micropowder and sodium-containing additive as raw materials, and performing blank making and molding; drying the blank, and sintering in a high-temperature kiln or an electric furnace at a maximum sintering temperature of 1650-1700 ℃; the sodium-containing additive and the impurity phase at the grain boundary form a liquid phase to dissolve the magnesia-alumina spinel and slowly crystallize, and flaky NMA grows at the grain boundary to separate the grain boundary through epitaxial growth at the grain boundary.
2. The method for preparing the high thermal shock magnesia-alumina spinel refractory with flaky crystals at grain boundaries according to claim 1, which is characterized in that: the aluminum content in the sintered magnesia-alumina spinel is 75% -78%.
3. The method for preparing the high thermal shock magnesia-alumina spinel refractory with flaky crystals at grain boundaries according to claim 1, which is characterized in that: the sodium-containing additive is one or more of NaCO 3、NaHCO3, naCl and NaF.
4. The method for preparing the high thermal shock magnesia-alumina spinel refractory with flaky crystals at grain boundaries according to claim 1, which is characterized in that: the precipitated flaky crystal is Mg-beta' -Al 2O3, which is limited by a growth space and is positioned at the grain boundary.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434492A (en) * | 2008-12-01 | 2009-05-20 | 瑞泰科技股份有限公司 | Large-sized special-shaped composite magnesium aluminate spinel product and technique for producing the same |
| CN103011885A (en) * | 2013-01-07 | 2013-04-03 | 中钢集团洛阳耐火材料研究院有限公司 | Magnesium aluminate spinel light refractory castable and production method thereof |
| CN113636852A (en) * | 2021-09-23 | 2021-11-12 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of spherical shell-sponge structure calcium hexaluminate-magnesia-alumina spinel complex phase material |
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| DE102004007062B4 (en) * | 2004-02-13 | 2007-08-02 | Refractory Intellectual Property Gmbh & Co. Kg | Offset for making a refractory ceramic product and method of making the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434492A (en) * | 2008-12-01 | 2009-05-20 | 瑞泰科技股份有限公司 | Large-sized special-shaped composite magnesium aluminate spinel product and technique for producing the same |
| CN103011885A (en) * | 2013-01-07 | 2013-04-03 | 中钢集团洛阳耐火材料研究院有限公司 | Magnesium aluminate spinel light refractory castable and production method thereof |
| CN113636852A (en) * | 2021-09-23 | 2021-11-12 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of spherical shell-sponge structure calcium hexaluminate-magnesia-alumina spinel complex phase material |
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