CN111925204B - Preparation method of magnesia-alumina spinel refractory material - Google Patents
Preparation method of magnesia-alumina spinel refractory material Download PDFInfo
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- CN111925204B CN111925204B CN202010853133.9A CN202010853133A CN111925204B CN 111925204 B CN111925204 B CN 111925204B CN 202010853133 A CN202010853133 A CN 202010853133A CN 111925204 B CN111925204 B CN 111925204B
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- spinel
- magnesium aluminate
- refractory material
- aluminum ash
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 57
- 239000011029 spinel Substances 0.000 title claims abstract description 57
- 239000011819 refractory material Substances 0.000 title claims abstract description 23
- 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 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- -1 magnesium aluminate Chemical class 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000003232 water-soluble binding agent Substances 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 235000001055 magnesium Nutrition 0.000 claims description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 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
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 235000012245 magnesium oxide Nutrition 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 235000012254 magnesium hydroxide Nutrition 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 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 description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000000748 compression moulding Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009875 water degumming Methods 0.000 description 1
Classifications
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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
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
- C04B35/6265—Thermal treatment of powders or mixtures thereof other than sintering involving reduction or oxidation
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- 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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- 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
- C04B35/6268—Thermal treatment of powders or mixtures thereof other than sintering characterised by the applied pressure or type of atmosphere, e.g. in vacuum, hydrogen or a specific oxygen pressure
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Abstract
The invention discloses a preparation method of a magnesia-alumina spinel refractory material, and aims to solve the technical problems of high equipment requirement, high energy consumption and short service life of equipment in the prior art due to volume expansion in the spinel crystal phase generation process. The preparation method of the spinel refractory material comprises the following steps: preparing a mixed material by taking aluminum ash, a magnesium raw material and an impurity removing agent; grinding the obtained mixed material; calcining the mixture in an oxygen-enriched environment by taking air as a combustion-supporting medium to obtain active magnesium aluminate spinel powder; grinding the obtained active magnesium aluminate spinel powder; adding a water-soluble binder solution and uniformly stirring; pressing into a blank, and sintering for the second time to obtain the spinel refractory material. According to the invention, the magnesium aluminate spinel is synthesized by adopting an aluminum ash two-step method, the active magnesium aluminate spinel powder is synthesized firstly, and then the spinel refractory material is prepared by compression molding and secondary sintering, so that volume expansion does not exist, the harmless and resource utilization of the aluminum ash is realized, the metal aluminum in the aluminum ash is combusted to release heat, and the production energy consumption of the active magnesium aluminate spinel powder is reduced.
Description
Technical Field
The invention relates to the technical field of refractory materials, in particular to a preparation method of a magnesia-alumina spinel refractory material.
Background
The aluminum ash is waste generated in the industrial production process of aluminum, mainly comprises simple substance aluminum, aluminum compounds, silicon oxide, magnesium oxide, sodium salt, potassium salt, fluoride salt, titanium oxide and the like, and has toxicity and inflammability. Scum generated on the surface of the melt in the processes of transferring, purifying and impurity removing of the melt in the electrolytic aluminum process, scum (salt slag and aluminum ash) generated on the surface of the melt in the processes of transferring, purifying and impurity removing of the waste aluminum smelting melt, and salt slag and secondary aluminum ash generated in the process of recovering metal aluminum from aluminum ash and aluminum slag by a molten salt method are listed in 2019 edition national hazardous waste records. According to statistics, each 1 ton of aluminum is produced, 15-30 kg of aluminum ash is probably generated, the domestic aluminum yield in 2019 is 3500 ten thousand tons, the generated aluminum ash is about 52.5-105 ten thousand tons, and the harmlessness and the resource utilization of the aluminum ash are problems which are urgently needed to be solved in the aluminum industrial production.
On the other hand, the magnesia-alumina spinel is a high-quality alkaline refractory material, has high melting point, high strength, good thermal conductivity, good stability and good slag resistance, and is widely applied to the fields of ladle castables, ladle lining bricks, cement rotary kilns and the like. The magnesia-alumina spinel refractory material synthesized by one-step method along with 6-8% volume expansion in the spinel crystal phase generation process needs higher temperature to densify, and has higher requirement on equipment, large energy consumption and short service life of the equipment.
Disclosure of Invention
The invention aims to provide a preparation method of a magnesia-alumina spinel refractory material, which aims to realize harmless and resource utilization of aluminum ash and solve the technical problems of high requirement on equipment, high energy consumption and short service life of equipment in the spinel crystal phase generation process accompanied by volume expansion in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a magnesia-alumina spinel refractory material is designed, and comprises the following steps:
(1) Mixing 60-85% of aluminum ash, 15-40% of magnesium raw material and 1-2% of impurity removing agent by mass percent to prepare a mixed material, and grinding the mixed material to 200-250 meshes;
(2) Calcining at 1300-1450 ℃ in an oxygen-enriched environment by taking air as a combustion-supporting medium to obtain active magnesium aluminate spinel powder;
(3) Grinding the obtained active magnesium aluminate spinel powder to 200-325 meshes; adding a water-soluble binder solution according to 1-3% of the weight of the active magnesium aluminate spinel powder, and uniformly stirring;
(4) Pressing the mixture into a blank under the pressure of 200-325 MPa, and sintering the blank for the second time to obtain the magnesia-alumina spinel refractory material.
Preferably, in the step (1), the aluminum ash contains 5 to 15 mass percent of Al and 5 to 15 mass percent of Al 2 O 3 50～75%、AlN 10～25%、SiO 2 ≤2%、Fe 2 O 3 ≤1.5%、CaO≤1.2%。
Preferably, in the step (1), the magnesian raw material is at least one of magnesite, light burned magnesite, periclase and magnesium hydroxide.
Preferably, in the step (1), the impurity removing agent is at least one of ammonium fluoride, ammonium chloride, aluminum fluoride and ammonium carbonate; the impurity removing agent can rapidly and thoroughly remove sodium salt, potassium salt and other impurities in the aluminum ash, and simultaneously promotes aluminum nitride in the aluminum ash to be rapidly oxidized and denitrified to generate nontoxic and harmless nitrogen, so that the aluminum ash is environment-friendly and pollution-free.
Preferably, in the step (2), the oxygen content of the rich oxygen is controlled to be 5-15%; the calcination time is controlled to be 0.5-1 h.
Preferably, in the step (3), the water-soluble binder is at least one of polyvinyl alcohol of 1.
Preferably, in the step (4), during sintering, the temperature is increased to 100-200 ℃ at the speed of 10-15 ℃/h, the moisture in the blank is removed, then the temperature is rapidly increased to 1000-1100 ℃ at the speed of 20-25 ℃/h, the binder is removed, finally the temperature is increased to 1500-1600 ℃ at the speed of 10-15 ℃/h, and the temperature is kept for 6-8 h, so that the blank is gradually densified.
In the production process, various waste gases are collected by fully utilizing the prior art means and equipment, the waste gases are preheated by secondary utilization, and the tail gases after harmless treatment reach the standard and are discharged.
Compared with the prior art, the invention has the main beneficial technical effects that:
1. according to the invention, the magnesium aluminate spinel is synthesized by adopting an aluminum ash two-step method, the active magnesium aluminate spinel powder is synthesized firstly, and then the spinel refractory material is prepared by compression molding and secondary sintering, so that volume expansion does not exist, the harmless and resource utilization of the aluminum ash can be realized, meanwhile, the metallic aluminum in the aluminum ash is combusted to release heat, and the energy consumption of the active magnesium aluminate spinel powder can be reduced.
2. According to the invention, the impurity removal auxiliary agent is utilized to gasify NaCl and KCl in the aluminum ash and separate the gasified NaCl and KCl from the aluminum ash, so that impurities such as sodium salt, potassium salt and the like in the aluminum ash can be rapidly and thoroughly removed, and the prepared active magnesium aluminate spinel powder is low in impurity content; the NaCl and the KCl are gasified and condensed to become solid for recycling, and the solid can be compounded into an aluminum water refining agent for recycling after being recycled; simultaneously, the aluminum nitride in the aluminum ash is oxidized and denitrified at high temperature to generate nontoxic and harmless nitrogen (4AlN + 3O) 2 =2Al 2 O 3 +2N 2 ) And is environment-friendly and pollution-free.
3. In the oxygen-enriched high-temperature calcination process, the combustion heat release of the metal aluminum remained in the aluminum ash is utilized, the energy consumption is low, namely, the metal aluminum simple substance is combusted to generate a large amount of heat, and a heat source is provided for the calcination: 4Al +3O 2 =2Al 2 O 3 。
4. In the traditional technology, oxygen-enriched combustion replaces air with pure oxygen to carry out fuel combustion, the fuel combustion speed is high, the combustion is sufficient, the flame temperature is high, the smoke is low in black toxicity, and part of smoke is required to be recycled; the invention uses air as combustion-supporting medium, and provides enough surplus oxygen in the fuel combustion process to make the fuel fully burn, and the excess oxygen makes the solid carbon in the carbon slag fully burn.
5. The invention obviously reduces the sintering temperature of the spinel refractory material; the requirement on equipment is low, and the service life of the equipment is prolonged; the harmless and resource utilization of the aluminum ash is realized; meanwhile, the comprehensive cost is reduced.
Detailed Description
The following examples are given to illustrate specific embodiments of the present invention, but are not intended to limit the scope of the present invention in any way.
The starting materials referred to in the following examples are, unless otherwise specified, all commercially available conventional starting materials; the test methods or detection methods are conventional methods unless otherwise specified.
Example 1: preparation method of magnesia-alumina spinel refractory material
1# aluminum ash and magnesite are selected to prepare spinel by a two-step method: wherein the 1# aluminum ash component: 5% of Al, al 2 O 3 67%、AlN 15%、SiO 2 1.2%、Fe 2 O 3 0.5 percent of CaO, 0.8 percent of NaCl and KCl, mgCO in magnesite 3 The content is 98.7 percent.
Weighing 60 parts of aluminum ash and 40 parts of magnesite, adding 1.5 parts of ammonium fluoride, ball-milling the mixture to 200 meshes, calcining for 2 hours at 1350 ℃ in an environment with oxygen content of 5%, and cooling to obtain active magnesium aluminate spinel powder.
Grinding active magnesium aluminate spinel powder to 325 meshes, adding a sodium hydroxypropyl methylcellulose aqueous solution (the ratio of solute to water is 1; rapidly heating to 1000 ℃ at the speed of 25 ℃/h, and removing the binder; heating to 1600 ℃ at the temperature of 15 ℃/h to gradually densify the blank; and preserving the heat at 1600 ℃ for 6h to finish densification.
Example 2: preparation method of magnesia-alumina spinel refractory material
2# aluminum ash and magnesium hydroxide are selected to prepare spinel by a two-step method: wherein the 2# aluminum ash component: 10% of Al, al 2 O 3 50%、AlN 20%、SiO 2 1.8%、Fe 2 O 3 1.5 percent, caO 1.2 percent, naCl and KCl 12 percent and the purity of the magnesium hydroxide is 99 percent.
Weighing 70 parts of aluminum ash and 30 parts of magnesium hydroxide, adding 2 parts of ammonium carbonate, ball-milling the mixture to 250 meshes, calcining for 5 hours at 1400 ℃ in an environment with oxygen content of 5%, and cooling to obtain the active magnesium-aluminum spinel powder.
Grinding active magnesium aluminate spinel powder to 325 meshes, adding a polyvinyl alcohol aqueous solution (the ratio of solute to water is 1: 100) with the weight of the active magnesium aluminate spinel powder being 1.5%, uniformly stirring, forming under the pressure of 200Mpa, heating to 150 ℃ at the speed of 10 ℃/h, and removing water in a blank; rapidly heating to 1000 ℃ at the speed of 25 ℃/h, and removing the binder; heating to 1580 ℃ at the temperature of 15 ℃/h to gradually densify the blank; and preserving the heat at 1580 ℃ for 8 hours to finish densification.
Example 3: preparation method of magnesia-alumina spinel refractory material
Selecting 3# aluminum ash and light-burned magnesia to prepare spinel by a two-step method: wherein the 3# aluminum ash component: 8% of Al, al 2 O 3 55%、AlN 13%、SiO 2 2%、Fe 2 O 3 0.5 percent, caO 0.9 percent, naCl and KCl 15 percent, and the purity of the light-burned magnesite is 99 percent.
Weighing 85 parts of aluminum ash and 15 parts of light-burned magnesia, adding 1.5 parts of ammonium chloride, ball-milling the mixture to 250 meshes, calcining for 3 hours at 1450 ℃ in an environment with 10% of oxygen content, and cooling to obtain the active magnesium aluminate spinel powder.
Grinding active magnesium aluminate spinel powder to 325 meshes, adding waste paper pulp liquid (the concentration is 0.5%) of which the weight is 2% of that of the active magnesium aluminate spinel powder, uniformly stirring, forming under the pressure of 300Mpa, heating to 150 ℃ at the speed of 10 ℃/h, and removing water in a blank; rapidly heating to 1000 ℃ at the speed of 20 ℃/h, and removing the binder; heating to 1500 ℃ at the temperature of 15 ℃/h to gradually densify the blank; preserving heat for 8h at 1500 ℃ to finish densification.
Test example:
the spinel refractories prepared in examples 1 to 3 were sampled and Al was measured 2 O 3 、MgO、SiO 2 、 Fe 2 O 3 、CaO、Na 2 O+K 2 O content, bulk density.
The detection method is GB/T5069 chemical analysis method for magnesium-aluminum series refractory materials, and GB/T2998 test method for volume density and true porosity of shaped heat-insulating refractory products.
The results are shown in Table 1.
TABLE 1 spinel refractory index
| Al 2 O 3 % | MgO% | SiO 2 % | Fe 2 O 3 % | CaO% | K 2 O+Na 2 O% | Bulk density g/cm 3 | |
| Example 1 | 72 | 23.7 | 0.9 | 0.38 | 0.6 | 0.4 | 3.4 |
| Example 2 | 72.2 | 22.8 | 1.4 | 1.2 | 0.8 | 0.3 | 3.45 |
| Example 3 | 76.5 | 18.6 | 1.7 | 0.42 | 0.7 | 0.15 | 3.5 |
As can be seen from Table 1, the product index obtained by the invention is superior to that of sintered alumina-grade magnesium aluminate spinel in GBT26564-2011 magnesium aluminate spinel, and is close to that of sintered alumina and magnesium aluminate spinel.
The present invention is explained in detail above with reference to examples; however, those skilled in the art will understand that various changes and modifications can be made in the above embodiments without departing from the scope of the present invention, and equivalent substitutions for related steps and materials can be made to form a plurality of embodiments, which are common variations of the present invention and will not be described in detail herein.
Claims (6)
1. The preparation method of the magnesia-alumina spinel refractory material is characterized by comprising the following steps:
(1) Mixing 60-85% of aluminum ash, 15-40% of magnesium raw material and 1-2% of impurity removing agent by mass percent to prepare a mixed material, and grinding the mixed material to 200-250 meshes; the impurity removing agent is at least one of ammonium fluoride, ammonium chloride and ammonium carbonate;
(2) Calcining at 1300-1450 ℃ in an oxygen-enriched environment by taking air as a combustion-supporting medium to obtain active magnesium aluminate spinel powder;
(3) Grinding the obtained active magnesium aluminate spinel powder to 200-325 meshes, adding a water-soluble binder solution according to 1-3% of the weight of the active magnesium aluminate spinel powder, and uniformly stirring;
(4) Pressing the mixture into a blank under the pressure of 200-325 MPa, and performing secondary sintering to obtain the spinel refractory material.
2. The method for preparing the magnesia-alumina spinel refractory according to claim 1, wherein in the step (1), the aluminum ash contains 5 to 15 mass percent of Al and 5 to 15 mass percent of Al 2 O 3 50～75%、AlN 10～25%、SiO 2 ≤2%、Fe 2 O 3 ≤1.5%、CaO≤1.2%。
3. The process of claim 1, wherein in the step (1), the magnesia raw material is at least one of magnesite, light burned magnesite, periclase and magnesium hydroxide.
4. The method for preparing the magnesia-alumina spinel refractory according to claim 1, wherein in the step (2), the oxygen content in the oxygen-rich environment is controlled to be 5-15%; the calcination time is controlled to be 0.5 to 1 hour.
5. The preparation method of the magnesia-alumina spinel refractory material according to claim 1, wherein in the step (3), the water-soluble binder is polyvinyl alcohol or an aqueous solution of at least one of pulp powder, hydroxypropyl methylcellulose and hydroxypropyl methylcellulose sodium, wherein the mass ratio of the solute to the solvent is 1.
6. The method for preparing the magnesia-alumina spinel refractory according to claim 1, wherein in the step (4), during sintering, the temperature is first raised to 100-200 ℃ at a heating rate of 10-15 ℃/h, then rapidly raised to 1000-1100 ℃ at a heating rate of 20-25 ℃/h, finally raised to 1500-1600 ℃ at a heating rate of 10-15 ℃/h, and kept at 1500-1600 ℃ for 6-8 h.
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| CN114180953A (en) * | 2021-12-01 | 2022-03-15 | 攀枝花钢城集团有限公司 | Method for synthesizing magnesia-alumina spinel from waste magnesium and aluminum-carbon bricks and magnesia-alumina spinel |
| CN114835504B (en) * | 2022-05-06 | 2023-04-25 | 北京科技大学 | Method for preparing wear-resistant high-temperature-resistant microporous corundum-spinel castable |
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