CN112266240A - Method for synthesizing aluminum-rich spinel by low-temperature solid-phase reaction - Google Patents
Method for synthesizing aluminum-rich spinel by low-temperature solid-phase reaction Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 231
- 239000011029 spinel Substances 0.000 title claims abstract description 231
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 140
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 119
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 88
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000001354 calcination Methods 0.000 claims abstract description 49
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000001095 magnesium carbonate Substances 0.000 claims description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 8
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 8
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000005309 metal halides Chemical class 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- 229910001507 metal halide Inorganic materials 0.000 claims description 6
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 abstract description 62
- 229910052593 corundum Inorganic materials 0.000 abstract description 40
- 239000010431 corundum Substances 0.000 abstract description 39
- 239000002893 slag Substances 0.000 abstract description 18
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 abstract description 17
- 239000011819 refractory material Substances 0.000 abstract description 13
- 238000005245 sintering Methods 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 230000035515 penetration Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 20
- 238000002050 diffraction method Methods 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- -1 magnesium aluminate Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
- C04B35/443—Magnesium aluminate spinel
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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- Chemical & Material Sciences (AREA)
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- Thermal Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to the field of refractory materials, and particularly relates to a method for synthesizing aluminum-rich spinel by low-temperature solid-phase reaction. The method specifically comprises the following steps: firstly, 80-90 parts of alumina raw material, 10-20 parts of magnesia raw material, 0.5-2 parts of magnesia-alumina spinel micro powder and 0.5-3 parts of additive are mixed according to parts by weight and are co-ground until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1000-1500 ℃ for calcination; and finally, keeping the calcination temperature for 3 to 12 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. The low-temperature synthesis process is adopted, the aluminum-rich spinel synthesized by low-temperature calcination has fine crystal grains and high lattice defect degree, and the prepared aluminum-rich spinel powder has high activity. The prepared aluminum-rich spinel does not contain beta alumina or impurity phases such as free magnesia and the like, and the content of alumina in the aluminum-rich spinel reaches 80-90%. When the prepared aluminum-rich spinel powder is used in corundum spinel castable, the powder has the advantages of high sintering strength and strong slag penetration resistance.
Description
Technical Field
The invention belongs to the field of refractory materials, and particularly relates to a method for synthesizing aluminum-rich spinel by low-temperature solid-phase reaction.
Background
The magnesium aluminate spinel structure is cubic system, and the unit cell is composed of 32 cubic close packed O2-16 Al in the octahedral voids3+And 8 Mg in tetrahedral voids2+And (4) forming. Each O is2-There are 4 metal coordinating ions, 3 of which are in the octahedron and the remaining 1 in the tetrahedron, and remain electrically neutral. Theoretically, the spinel consists of 28.3 mass percent of MgO and 71.7 mass percent of Al2O3MgO and Al at high temperature2O3Can be dissolved into magnesium aluminate spinel to form magnesium-rich spinel and aluminum-rich spinel. Wherein the content of the orthospinel alumina is 70-75%, the content of the magnesium-rich spinel alumina is 60-70%, and the content of the aluminum-rich spinel alumina is more than 75%. The magnesium aluminate spinel material has high melting point (2135 deg.C), and small thermal expansion coefficient (7.6 × 10 at 20-1000 deg.C)-6The refractory material has the advantages of low thermal conductivity (5.82W/(m.K) at 1000 ℃), stable chemical properties, strong resistance to erosion of various melts at high temperature, high strength, high hardness, high temperature resistance and wear resistance, and excellent performance, so the refractory material is widely applied to thermal equipment such as steel ladles, electric furnace tops, external refining furnaces, lime kilns, calcining kilns, large cement rotary kilns and the like.
At present, orthospinel is generally added into the corundum spinel castable, the synthesis temperature is very high (more than 1500 ℃), the activity of the obtained product is low, and the sintering strength and the slag resistance of the prepared corundum spinel refractory material are general.
For the aluminum-rich spinel, more aluminum oxide is dissolved in the aluminum-rich spinel, so that the crystal lattice of the spinel is defective, and the later sintering activity is high. When the aluminum-rich spinel is used in the refractory material, the aluminum-rich spinel can better capture substances such as FeO, MnO, CaO and the like in the molten slag, change the components of the molten slag on the contact surface with the refractory material, improve the viscosity of the slag and improve the slag penetration resistance of the refractory material.
When the conventional synthesis process is used for producing the aluminum-rich spinel, volume expansion is generated, sintering is not facilitated, the recrystallization capability is weak, the high-strength and high-performance aluminum-rich spinel product is required to be prepared, the synthesis temperature is more than 1500 ℃, the content of alumina in the prepared spinel is generally only within 72-78% and hardly reaches more than 80%, the corresponding degree of lattice defects is low, the solid solution amount of the alumina cannot be maximally improved, and meanwhile, the performance of the aluminum-rich spinel cannot be maximally exerted. And the impurity removal effect in the synthesis process is poor, sodium oxide impurities in the raw materials are easy to form beta-alumina, and the generation rate of the magnesium aluminate spinel is reduced. When the prepared aluminum-rich spinel is used in corundum spinel castable, the slag resistance and the sintering performance of the aluminum-rich spinel cannot reach the optimal level.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for synthesizing aluminum-rich spinel by low-temperature solid-phase reaction, wherein the aluminum oxide content of the aluminum-rich spinel prepared by the method reaches 80-90%, the lattice defect is large, and the purity of the spinel is high. When the prepared aluminum-rich spinel powder is used in corundum spinel castable, the powder has the advantages of high sintering strength and strong slag penetration resistance.
The method mainly comprises the steps of taking pretreated high-purity magnesium oxide, industrial alumina and calcined alumina as main synthetic raw materials, adding spinel crystal seeds and a specific additive, uniformly activating the mixed raw materials through a specific mixing and grinding process, placing the mixed raw materials in a high-temperature kiln for calcination, wherein the required calcination temperature is 1000-1500 ℃, then preserving heat for 3-12 hours at the calcination temperature, and finally cooling to obtain the aluminum-rich spinel powder. The content of alumina in the synthesized spinel powder can reach 80-90%, and the crystal face interval is reduced by about 5% (about)
). Grinding the synthesized rich-aluminum spinel powder to 1-5 μm to obtain corresponding rich-aluminum spinel micropowder.
One object of the present invention is to provide a method for synthesizing aluminum-rich spinel by low temperature solid phase reaction. The synthesis method comprises the following steps:
s1: mixing 80-90 parts of alumina raw material, 10-20 parts of magnesia raw material, 0.5-2 parts of magnesia-alumina spinel micro powder and 0.5-3 parts of additive by weight, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m;
s2: transferring the co-milled powder in the step S1 into a high-temperature kiln, and heating to 1000-1500 ℃ for calcination;
s3: keeping the calcination temperature of the step S2 for 3-12 hours, and naturally cooling or quickly cooling to normal temperature to obtain the aluminum-rich spinel.
Further, the alumina content of the aluminum-rich spinel is 80-90%, and the aluminum-rich spinel is ground to the particle size of 1-5 μm, so that the aluminum-rich spinel micro powder can be obtained.
Further, the alumina raw material is one or two of industrial alumina powder, calcined alpha alumina powder and aluminum hydroxide powder; the mass content of sodium oxide in the alumina raw material is less than 1%.
Further, the magnesium oxide raw material is one or a combination of two of magnesium hydroxide, light-burned magnesite and magnesite; after the magnesium oxide raw material is subjected to pyrolysis, the mass content of solid impurities is less than 3%.
Furthermore, the magnesia-alumina spinel micro powder is normal spinel, and the particle size is 0.5-1 μm.
Further, the additive is one or two of boric acid, borate and metal halide.
Further, the borate is boric anhydride, and the metal halide is one of magnesium chloride, aluminum chloride, magnesium fluoride and aluminum fluoride.
Further, the high-temperature kiln is one of a tunnel kiln, a shuttle kiln, a rotary kiln and a shaft kiln.
In the invention, the addition of the additive has the following three functions:
1) has the function of removing impurity sodium oxide in the raw materials of aluminum oxide and magnesium oxide, and can effectively reduce beta-Al in the aluminum-rich spinel powder2O3Without free magnesium oxide phase. Due to beta-Al2O3The aluminum-rich spinel is a composite oxide of sodium oxide and aluminum oxide, and the impurity sodium oxide can interfere the reaction of the aluminum oxide and the magnesium oxide to generate the aluminum-rich spinel, so that the purity of the generated aluminum-rich spinel is reduced. Adding boric acid (salt) or metal halide, reacting with impurity sodium oxide at high temperature, discharging generated gas, reducing sodium oxide content in reactant, and making magnesium oxide and aluminum oxide fully react. When the impurity sodium oxide is removed, the aluminum-rich spinel does not contain beta-Al2O3. The aluminum-rich spinel produced with the alumina surplus does not contain free magnesia phases.
2) The sintering temperature is reduced, and the generation rate of the aluminum-rich spinel is improved. The addition of the metal halide can lower the sintering temperature because the metal halide forms a molten salt at a certain temperature, and the aluminum oxide and the magnesium oxide which participate in the reaction have certain solubility in the molten salt, so that the reactants are mixed in a liquid phase on an atomic scale, and in addition, the reactants have higher diffusion speed in a liquid phase medium. The two effects can enable the synthesis reaction to be completed at lower temperature; the addition of boric acid (salt) can reduce the reaction sintering temperature on one hand, and on the other hand, the boric acid (salt) is dehydrated and converted into boron oxide at a certain temperature, so that the boric acid (salt) plays a role of a high-temperature adhesive and promotes the generation rate of the aluminum-rich spinel.
3) Promoting the solid solution of alumina into the aluminum-rich spinel and improving the degree of lattice defect. The introduction of the additive promotes the conversion of the raw material of the alumina from a gamma phase to an alpha phase, and the generated alpha phase alumina has high reaction activity and is easier to be dissolved in a spinel structure. The more solid solution of the alumina, the more defects and the smaller lattice constant; when the cationic vacancy is used in a refractory material, the cationic vacancy can better capture substances such as FeO, MnO, CaO and the like in molten slag, change the components of the molten slag on the contact surface with the refractory material, improve the viscosity of the slag and improve the slag corrosion resistance of the refractory material.
In the invention, the magnesia-alumina spinel micro powder is added as the seed crystal to form crystal nucleus in the reaction process and promote the generation of the rich-alumina spinel.
Another object of the present invention is to provide an aluminum-rich spinel prepared by low temperature solid phase reaction.
The synthesized rich-aluminum spinel does not contain beta alumina or impurity phases such as free magnesia, the content of alumina in the rich-aluminum spinel reaches 80-90%, the lattice defect is large, the solid solution amount of alumina is extremely large, and the purity of the spinel is high. When the obtained aluminum-rich spinel powder is applied to corundum spinel castable, the aluminum-rich spinel powder has the advantages of high sintering strength, and strong slag corrosion resistance and slag penetration resistance.
Compared with the prior art, the invention has the following advantages:
1) the invention adopts a low-temperature synthesis process, the aluminum-rich spinel synthesized by low-temperature calcination has fine crystal grains and high lattice defect degree, and the prepared aluminum-rich spinel powder has high activity; in addition, the calcined aluminum-rich spinel powder is easier to grind into micron-level micro powder, so that the surface activity is increased, and the high-temperature sintering and slag resistance of the refractory material are promoted, thereby improving the service performance of the refractory material.
2) The aluminum-rich spinel synthesized by the low-temperature process does not contain beta alumina or impurity phases such as free magnesia and the like, the content of alumina in the aluminum-rich spinel reaches 80-90%, the lattice defect is large, the solid solution amount of alumina is extremely large, and the spinel has high purity and good application prospect.
Drawings
FIG. 1 shows alumina feedstock: XRD diffractogram of alumina-rich spinel micropowder prepared when magnesia raw material is 90: 10.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clearly apparent, the technical solutions of the present invention are further described in detail below with reference to examples, and it should be understood that the specific embodiments described in the present specification are only for explaining the present invention and are not intended to limit the present invention.
The aggregate (magnesium or aluminum, 0-8mm), magnesia-alumina spinel fine powder (200 meshes), magnesia-alumina spinel fine powder (325 meshes), active alumina micro powder (1-2 mu m), pure calcium aluminate cement and water reducing agent used by the corundum spinel castable can be obtained commercially.
The magnesium aluminate spinel micro powder (the normal spinel micro powder is 0.5-1 mu m) used for synthesizing the aluminum-rich spinel, the magnesium oxide raw material, the aluminum oxide raw material and the additive can be obtained commercially; in the comparative example, the magnesia alumina spinel micro powder and the aluminum-rich spinel micro powder are prepared by the preparation method.
The low-temperature synthesis method of the aluminum-rich spinel comprises the following steps:
s1: mixing 80-90 parts of alumina raw material, 10-20 parts of magnesia raw material, 0.5-2 parts of magnesia-alumina spinel seed crystal and 0.5-3 parts of additive by weight, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m;
s2: transferring the co-milled powder in the step S1 into a high-temperature kiln, and heating to 1000-1500 ℃ for calcination;
s3: keeping the calcination temperature of the step S2 for 3-12 hours, and naturally cooling or quickly cooling to normal temperature to obtain the aluminum-rich spinel.
The alumina content of the rich-aluminum spinel is 80-90%, and the rich-aluminum spinel is ground to the particle size of 1-5 mu m, so that the rich-aluminum spinel micro powder can be obtained.
The process for synthesizing the aluminum-rich spinel is further described below with reference to specific examples, while the resulting aluminum-rich spinel is characterized.
Example 1
Firstly, mixing 10 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 90 parts by weight of a mixture of industrial alumina powder and calcined alpha alumina powder, 3 parts by weight of normal spinel seed crystal, 2 parts by weight of boric acid and magnesium chloride, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1000-1100 ℃ for calcination; and finally, keeping the calcination temperature for 8-10 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. Grinding the aluminum-rich spinel to a particle size of 1.5-3 μm to obtain the aluminum-rich spinel micro powder.
XRD diffraction is carried out on the obtained aluminum-rich spinel micro powderThrough analysis, the synthesized aluminum-rich spinel micro powder does not contain beta alumina phase, free magnesia phase, 45 percent of aluminum-rich spinel phase, 55 percent of corundum phase and about 5 percent of crystal face interval (about)
) The diffraction pattern is shown in FIG. 1.
Example 2
Firstly, mixing 10 parts by weight of light-burned magnesia, 90 parts by weight of calcined alpha alumina powder, 0.5 part by weight of normal spinel seed crystal and 0.5 part by weight of boric anhydride, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1400-1500 ℃ for calcination; and finally, keeping the calcination temperature for 4 to 6 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. And grinding the aluminum-rich spinel to a particle size of 2-5 mu m to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain a beta alumina phase and a free magnesia phase, and has 48% of rich-aluminum spinel phase content and 52% of corundum phase content.
Example 3
Firstly, mixing 10 parts by weight of a mixture of magnesite and light-burned magnesite, 90 parts by weight of a mixture of industrial alumina powder and aluminum hydroxide powder, 1.5 parts by weight of n-spinel crystal seed, 1 part by weight of boric anhydride and aluminum fluoride, and then co-grinding until the particle size of the raw materials is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1200-1300 ℃ for calcination; and finally, keeping the calcination temperature for 6 to 8 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. And grinding the aluminum-rich spinel to a particle size of 1-4 mu m to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain beta alumina phase and free magnesia phase, and has 47% of rich-aluminum spinel phase content and 53% of corundum phase content.
Example 4
Firstly, mixing 15 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 85 parts by weight of a mixture of industrial alumina powder and calcined alpha alumina powder, 3 parts by weight of normal spinel seed crystal, 2 parts by weight of boric acid and aluminum chloride, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1000-1100 ℃ for calcination; and finally, keeping the calcination temperature for 8-10 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. Grinding the aluminum-rich spinel to a particle size of 1.5-3 μm to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain beta alumina phase and free magnesia phase, the content of the rich-aluminum spinel phase is 53%, and the content of corundum phase is 47%.
Example 5
Firstly, mixing 15 parts of magnesite, 85 parts of industrial alumina powder, 0.5 part of normal spinel crystal seed and 0.5 part of boric acid in parts by weight, and then co-grinding until the particle size of the raw materials is within the range of 5-20 μm; transferring the co-milled powder into a high-temperature kiln, and heating to 1400-1500 ℃ for calcination; and finally, keeping the calcination temperature for 4 to 6 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. And grinding the aluminum-rich spinel to a particle size of 2-4 mu m to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain beta alumina phase and free magnesia phase, and has 56% of rich-aluminum spinel phase and 44% of corundum phase.
Example 6
Firstly, mixing 15 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 85 parts by weight of a mixture of industrial alumina powder and aluminum hydroxide powder, 1.5 parts by weight of n-spinel seed crystal, 1 part by weight of boric anhydride and magnesium chloride, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1200-1300 ℃ for calcination; and finally, keeping the calcination temperature for 6 to 8 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. And grinding the aluminum-rich spinel to a particle size of 2-4 mu m to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain beta alumina phase and free magnesia phase, and contains 55% of rich-aluminum spinel phase and 45% of corundum phase.
Example 7
Firstly, mixing 20 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 80 parts by weight of a mixture of industrial alumina powder and calcined alpha alumina powder, 3 parts by weight of normal spinel seed crystal, 2 parts by weight of boric anhydride and aluminum fluoride, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1000-1100 ℃ for calcination; and finally, keeping the calcination temperature for 8-10 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. Grinding the aluminum-rich spinel to a particle size of 1.5-3 μm to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain a beta alumina phase and a free magnesia phase, and has a content of the rich-aluminum spinel phase of 70% and a content of a corundum phase of 30%.
Example 8
Firstly, mixing 20 parts of magnesite, 80 parts of industrial alumina powder, 0.5 part of normal spinel crystal seed and 0.5 part of aluminum chloride in parts by weight, and then co-grinding until the particle size of the raw materials is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1400-1500 ℃ for calcination; and finally, keeping the calcination temperature for 4 to 6 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. And grinding the aluminum-rich spinel to a particle size of 2-5 mu m to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain beta alumina phase and free magnesia phase, the content of the rich-aluminum spinel phase is 75%, and the content of corundum phase is 25%.
Example 9
Firstly, mixing 20 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 80 parts by weight of a mixture of calcined alpha alumina powder and aluminum hydroxide powder, 1.5 parts by weight of normal spinel seed crystal, 1 part by weight of boric acid and magnesium chloride, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1200-1300 ℃ for calcination; and finally, keeping the calcination temperature for 6 to 8 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. And grinding the aluminum-rich spinel to a particle size of 2-4 mu m to obtain the aluminum-rich spinel micro powder.
XRD diffraction analysis is carried out on the obtained rich-aluminum spinel micro powder, and the synthesized rich-aluminum spinel micro powder does not contain beta alumina phase and free magnesia phase, the content of the rich-aluminum spinel phase is 72 percent, and the content of corundum phase is 28 percent.
Comparative example 1
Firstly, mixing 28 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 72 parts by weight of a mixture of industrial alumina powder and calcined alpha alumina powder, 1.5 parts by weight of n-spinel seed crystal, 1 part by weight of boric acid and magnesium chloride, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m; transferring the co-milled powder into a high-temperature kiln, and heating to 1200-1300 ℃ for calcination; and finally, keeping the calcination temperature for 8-10 hours, and naturally cooling or quickly cooling the calcination temperature to the normal temperature to obtain the aluminum-rich spinel. Grinding the aluminum-rich spinel to a particle size of 1.5-3 μm to obtain the spinel micro powder.
XRD diffraction analysis is carried out on the obtained normal spinel micro powder, and the synthesized normal spinel micro powder does not contain a beta alumina phase and a free magnesia phase, and has 99% of aluminum-rich spinel phase and 1% of corundum phase.
The content of the alumina-rich spinel phase and the content of the corundum phase in the alumina-rich spinel micro powders synthesized in examples 1 to 9 were changed from those of the spinel micro powders, wherein the content of the corundum phase in the alumina-rich spinel micro powders was increased accordingly with the increase of the alumina content, so that the lattice defects of the alumina-rich spinel micro powders were large, and wherein the amount of solid solution of alumina was extremely large, and in addition, the spinel purity was also increased accordingly.
Comparative example 2
Preparing common magnesia-alumina spinel micro powder: firstly, mixing 15 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 85 parts by weight of industrial alumina powder and calcined alpha alumina powder, and 1.5 parts by weight of a mixture of normal spinel seed crystals, and then co-grinding until the particle size of the raw materials is within the range of 5-20 μm; transferring the co-milled powder into a high-temperature kiln, and heating to 1600-1700 ℃ for calcination; and finally keeping the temperature for 6 to 8 hours at the calcining temperature, and naturally cooling or quickly cooling the mixture to the normal temperature to obtain the common magnesia-alumina spinel fine powder. Grinding the common magnesia-alumina spinel fine powder to a particle size of 2-5 mu m.
XRD diffraction analysis is carried out on the common magnesia-alumina spinel micro powder, and the synthesized spinel micro powder contains 5% of beta alumina phase, 0.5% of free magnesia phase, 52% of alumina-rich spinel phase and 42.5% of corundum phase.
Comparative example 3
Preparing common magnesia-alumina spinel fine powder: firstly, mixing 15 parts by weight of a mixture of magnesium hydroxide and light-burned magnesia, 85 parts by weight of industrial alumina powder and calcined alpha alumina powder, and 1.5 parts by weight of a mixture of normal spinel seed crystals, and then co-grinding until the particle size of the raw materials is within the range of 5-20 μm; transferring the co-milled powder into a high-temperature kiln, and heating to 1200-1300 ℃ for calcination; and finally keeping the temperature for 6 to 8 hours at the calcining temperature, and naturally cooling or quickly cooling the mixture to the normal temperature to obtain the common magnesia-alumina spinel fine powder. Grinding the common magnesia-alumina spinel fine powder to a particle size of 2-5 mu m.
XRD diffraction analysis is carried out on the common magnesia-alumina spinel fine powder, and the synthesized spinel fine powder contains 5% of beta alumina phase, 1.3% of free magnesia phase, 48% of rich alumina spinel phase and 45.7% of corundum phase.
As can be seen from comparative examples 2 and 3, when no admixture is added, a higher temperature is required to synthesize the aluminum-rich spinel with a beta alumina phase, a free magnesia phase, and a reduced corundum phase content.
The aluminum-rich spinels prepared in examples 1 to 9 and the magnesia alumina spinel micropowder prepared in comparative examples 1 to 3 were applied to a corundum spinel castable according to the formula of the corundum spinel castable in table 1 below:
table 1 formula table of corundum spinel pouring material
The materials described in the table above were used to prepare corundum spinel castable according to conventional existing methods, and the obtained corundum spinel castable was subjected to performance tests, the results of which are shown in table 2.
TABLE 2 Performance test Table
As can be seen from table 2, compared with the magnesia alumina spinel micro powder in the corundum spinel castable in comparative examples 1 to 3, if the alumina-rich spinel micro powder in examples 1 to 9 is added, the performances of the obtained corundum spinel castable in all aspects are improved, and the corundum spinel castable added with the alumina-rich spinel micro powder in examples 1 to 9 has higher rupture strength at 1100 ℃, rupture strength at 1550 ℃ and water-cooling strength retention rate at 1100 ℃ for 0.5h 5 times than the proportion, which indicates that the alumina-rich spinel micro powder can improve the strength of the castable after firing when being used in the corundum spinel castable; in addition, the ratio of the penetration index of the corundum spinel castable added with the aluminum-rich spinel micro powder in the examples 1-9 to the penetration index of a slag-resistant experiment at 1550 ℃ for 3h is small, which shows that the aluminum-rich spinel micro powder can improve the slag penetration resistance of the corundum spinel castable when being used for the corundum spinel castable. In comparative examples 2 and 3, the performance of the corundum spinel castable was also reduced when the corundum spinel castable was used without adding additives. Meanwhile, as can be seen from the table, along with the increase of the content of alumina in the aluminum-rich spinel micro powder, when the aluminum-rich spinel micro powder is used in a corundum spinel castable, the slag penetration resistance and strength of corundum spinel are further improved. Therefore, the aluminum-rich spinel disclosed by the invention has wide application scenarios in corundum spinel castable materials.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (9)
1. A method for synthesizing aluminum-rich spinel by low-temperature solid-phase reaction is characterized in that: the synthesis method comprises the following steps:
s1: mixing 80-90 parts of alumina raw material, 10-20 parts of magnesia raw material, 0.5-2 parts of magnesia-alumina spinel micro powder and 0.5-3 parts of additive by weight, and then co-grinding until the particle size of the raw material is within the range of 5-20 mu m;
s2: transferring the co-milled powder in the step S1 into a high-temperature kiln, and heating to 1000-1500 ℃ for calcination;
s3: keeping the calcination temperature of the step S2 for 3-12 hours, and naturally cooling or quickly cooling to normal temperature to obtain the aluminum-rich spinel.
2. The method for synthesizing an aluminum-rich spinel by a low-temperature solid-phase reaction according to claim 1, wherein: the alumina content of the rich-aluminum spinel is 80-90%, and the rich-aluminum spinel is ground to the particle size of 1-5 mu m, so that the rich-aluminum spinel micro powder can be obtained.
3. The method for synthesizing an aluminum-rich spinel by a low-temperature solid-phase reaction according to claim 1, wherein: the alumina raw material is one or two of industrial alumina powder, calcined alpha alumina powder and aluminum hydroxide powder; the mass content of sodium oxide in the alumina raw material is less than 1%.
4. The method for synthesizing an aluminum-rich spinel by a low-temperature solid-phase reaction according to claim 1, wherein: the magnesium oxide raw material is one or two of magnesium hydroxide, light-burned magnesite and magnesite; after the magnesium oxide raw material is subjected to pyrolysis, the mass content of solid impurities is less than 3%.
5. The method for synthesizing an aluminum-rich spinel by a low-temperature solid-phase reaction according to claim 1, wherein: the magnesia-alumina spinel micro powder is normal spinel, has a particle size of 0.5-1 mu m and is used as a seed crystal.
6. The method for synthesizing an aluminum-rich spinel by a low-temperature solid-phase reaction according to claim 1, wherein: the additive is one or two of boric acid, borate and metal halide.
7. The method for synthesizing an aluminum-rich spinel by a low temperature solid phase reaction according to claim 6, wherein: the borate is boric anhydride, and the metal halide is one of magnesium chloride, aluminum chloride, magnesium fluoride and aluminum fluoride.
8. The method for synthesizing an aluminum-rich spinel by a low-temperature solid-phase reaction according to claim 1, wherein: the high-temperature kiln is one of a tunnel kiln, a shuttle kiln, a rotary kiln and a shaft kiln.
9. An aluminum-rich spinel, characterized by: the aluminum-rich spinel is prepared by the method for synthesizing the aluminum-rich spinel according to any one of claims 1-8 through low-temperature solid-phase reaction.
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