CN118184369A - Corundum-spinel refractory material taking ferrotitanium slag as main material and preparation method thereof - Google Patents
Corundum-spinel refractory material taking ferrotitanium slag as main material and preparation method thereof Download PDFInfo
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- CN118184369A CN118184369A CN202211603124.XA CN202211603124A CN118184369A CN 118184369 A CN118184369 A CN 118184369A CN 202211603124 A CN202211603124 A CN 202211603124A CN 118184369 A CN118184369 A CN 118184369A
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- slag
- corundum
- ferrotitanium
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- spinel refractory
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- 239000002893 slag Substances 0.000 title claims abstract description 83
- 229910001200 Ferrotitanium Inorganic materials 0.000 title claims abstract description 56
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 44
- 239000011029 spinel Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000011819 refractory material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000003723 Smelting Methods 0.000 claims abstract description 15
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 14
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 14
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 3
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 abstract description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 8
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 8
- 239000004571 lime Substances 0.000 abstract description 8
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000020169 heat generation Effects 0.000 abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000292 calcium oxide Substances 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical class [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 3
- 238000007133 aluminothermic reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a corundum-spinel refractory material taking titanium iron slag as a main material and a preparation method thereof. When slagging is carried out in the ferrotitanium smelting production process, light burned magnesia or magnesite is used as a slagging agent to replace the traditional calcium oxide slagging agent, ferrotitanium slag in a molten state is blown out, and is crushed into powder after cooling, so that corundum-spinel refractory raw materials taking the ferrotitanium slag as a main material are obtained. The refractory raw material can be directly used as the raw material in high-grade aluminum-magnesium spinel refractory materials, and the added value of ferrotitanium slag is higher than that of ferrotitanium slag generated by using a lime slag former. The preparation method has the advantages of simple process, energy conservation, environmental protection, low cost, stable components, high bonding strength, low heat generation and the like.
Description
Technical Field
The invention relates to the technical field of industrial waste recycling, in particular to a corundum-spinel refractory material taking ferrotitanium slag as a main material and a preparation method thereof.
Background
The titanium iron slag is slag generated when ferrotitanium alloy is smelted by a thermite method. The traditional process is to prepare ferrotitanium alloy by taking ilmenite as a main raw material, adopting metallic aluminum as a reducing agent and limestone as a slag former through aluminothermic reaction under the high temperature condition (generally above 1900 ℃), which is a widely used and mature industrial technical means at present. The slag and the ferrotitanium alloy are easy to separate due to different specific gravity. Most enterprises use the waste slag as the ingredients of building materials after being filled with industrial garbage or simply crushed, or replace the traditional alumina raw materials in the refractory industry after processing, and the utilization value is low.
The titanium iron slag also contains partial metal simple substance titanium and divalent titanium compound, the main components of the titanium iron slag are alumina and titanium-containing oxide, wherein the slag former can react with the alumina and the titanium oxide at high temperature generated by aluminothermic reaction to generate various phases, and the titanium iron slag can be directly used as a refractory raw material without treatment. The titanium iron slag has larger volume expansion at 1400 ℃ in actual use, and weight gain can occur, so that the high-temperature service performance of the material is reduced. Therefore, it is necessary to treat the calcium-containing phase to reduce the impurity and low-melting content when recovering the titanium slag as a refractory raw material.
The Chinese patent document CN1554778A discloses a low-titanium calcium aluminate and a preparation method thereof, which adopts industrial alumina and byproducts thereof, calcite or limestone, fluorite and feldspar as raw materials, and prepares the low-titanium calcium aluminate through crushing, mixing, melting, cooling, crushing and screening, wherein the material is used for replacing low-grade bauxite raw materials and has no good utilization value.
The Chinese patent document CN108484187A discloses a modified titanium calcium aluminate refractory raw material and a preparation method thereof, which takes waste residue titanium calcium aluminate generated during ferrotitanium alloy smelting (lime is taken as a slag former) as a main raw material, and improves the stability, sinterability, service performance and the like of the titanium calcium aluminate to a certain extent by means of presintering and secondary sintering by adding a proper amount of additives.
Disclosure of Invention
The invention aims to solve the technical problem of providing a corundum-spinel refractory raw material taking ferrotitanium slag as a main material and a preparation method thereof, wherein the refractory raw material can be directly used as a raw material in a high-grade aluminum-magnesium spinel refractory material, the added value of the ferrotitanium slag is higher than that of the ferrotitanium slag generated by using a lime slag former in the prior art, and the high added value utilization of the whole process product is realized. The preparation method has the advantages of simple process, energy conservation, environmental protection, low cost, stable components, high bonding strength, low heat generation and the like, can partially or even completely replace corundum and spinel raw materials in high-grade aluminum-magnesium spinel refractory material products, and is suitable for being used as refractory raw materials.
In order to solve the technical problems, the corundum-spinel refractory raw material composition taking the titanium slag as the main material comprises 72.0～80.0wt% Al2O3、15.0～20.0 wt % TiO2、3.0～8.0 wt %MgO、0～0.5 wt % Fe2O3 and 0-0.7-wt% SiO 2.
Further, the phase composition of the corundum-spinel refractory raw material comprises corundum, magnesia-alumina spinel and titanium oxide.
The preparation method of the corundum-spinel refractory material taking the titanium iron slag as the main material comprises the following steps:
step one, when slag formation is carried out in the ferrotitanium smelting production process, light burned magnesia or magnesite is used as a slag former;
smelting and deslagging according to a ferrotitanium production process or uncovering a slag cover after cooling, so that slag and iron are thoroughly separated;
and thirdly, crushing the cooled ferrotitanium slag to prepare the granularity meeting the production requirement of the refractory material, thereby obtaining the corundum-spinel refractory material.
Further, the mass percentage of MgO content in the light burned magnesia is more than 85.0%, the mass percentage of MgO content in the magnesite is more than 41.0%, and the granularity is 100 mesh screen blanking.
Further, the addition amount of the light burned magnesia or magnesite is 1-6% of the weight of ferrotitanium smelting ingredients.
The corundum-spinel refractory material taking the ferrotitanium slag as the main material and the preparation method adopt the technical scheme that the refractory material comprises alumina, magnesia-alumina spinel and titanium-containing oxide with certain components. When slagging is carried out in the ferrotitanium smelting production process, light burned magnesia or magnesite is used as a slagging agent to replace the traditional calcium oxide slagging agent, ferrotitanium slag in a molten state is blown out, and is crushed into powder after cooling, so that corundum-spinel refractory raw materials taking the ferrotitanium slag as a main material are obtained. The refractory raw material can be directly used as the raw material in high-grade aluminum-magnesium spinel refractory materials, and the added value of ferrotitanium slag is higher than that of ferrotitanium slag generated by using a lime slag former. The preparation method has the advantages of simple process, energy conservation, environmental protection, low cost, stable components, high bonding strength, low heat generation and the like.
Detailed Description
The corundum-spinel refractory raw material composition taking the titanium iron slag as the main material comprises 72.0～80.0wt% Al2O3、15.0～20.0 wt % TiO2、3.0～8.0 wt %MgO、0～0.5 wt % Fe2O3 and 0-0.7-wt% SiO 2.
Preferably, the corundum-spinel refractory raw material has the phase composition of corundum, magnesia-alumina spinel and titanium oxide.
The preparation method of the corundum-spinel refractory material taking the titanium iron slag as the main material comprises the following steps:
step one, when slag formation is carried out in the ferrotitanium smelting production process, light burned magnesia or magnesite is used as a slag former;
smelting and deslagging according to a ferrotitanium production process or uncovering a slag cover after cooling, so that slag and iron are thoroughly separated;
and thirdly, crushing the cooled ferrotitanium slag to prepare the granularity meeting the production requirement of the refractory material, thereby obtaining the corundum-spinel refractory material.
Preferably, the mass percentage of MgO content in the light burned magnesia is more than 85.0%, the mass percentage of MgO content in the magnesite is more than 41.0%, and the granularity is 100 mesh screen blanking.
Preferably, the addition amount of the light burned magnesia or magnesite is 1-6% of the weight of ferrotitanium smelting ingredients.
In the embodiment 1, when ferrotitanium alloy is smelted and produced, light burned magnesium oxide is utilized to replace the traditional lime slag former for slag formation, the addition amount of the light burned magnesium oxide is 2 percent of the total material amount, the ferrotitanium alloy is produced according to the production process of ferrotitanium alloy smelting, ferrotitanium slag in a molten state is discharged or cooled along with a furnace, and the recovery rate of ferrotitanium is 67.21 percent. And cooling the ferrotitanium slag, and crushing the ferrotitanium slag into raw materials with different granularity to obtain the corundum-spinel refractory raw material taking the ferrotitanium slag as a main material. The slag discharge during the process and the chemical composition analysis of the raw materials in different areas after cooling along with the furnace are shown in the table 1, and the phase composition of the raw materials is mainly alumina, magnesia-alumina spinel and titanium sesquioxide after analysis, the refractoriness is more than or equal to 1790 ℃, and the volume density is 3.46g/cm 3.
TABLE 1 analysis of chemical composition at different regions of slag sample
In the embodiment 2, during ferrotitanium alloy smelting production, magnesite is utilized to replace the traditional lime slag former for slag formation, the adding amount of the magnesite is 4.5% of the whole material amount, the ferrotitanium alloy smelting production process is adopted for production, the reaction is normal, a small amount of sodium chlorate is added for heat extraction, ferrotitanium slag in a molten state is discharged or cooled along with a furnace, and the recovery rate of ferrotitanium is 66.97%. And cooling the ferrotitanium slag, and crushing the ferrotitanium slag into raw materials with different granularity to obtain the corundum-spinel refractory raw material taking the ferrotitanium slag as a main material. The chemical analysis of slag discharge during the process and the ingredients of the raw materials in different areas after cooling along with the furnace are shown in table 2, and the phase composition of the raw materials is mainly alumina, magnesia-alumina spinel and titanium sesquioxide after analysis, and the refractoriness is more than or equal to 1790 ℃; the bulk density was 3.43g/cm 3.
TABLE 2 analysis of chemical composition at different regions of slag sample
In the above examples 1 and 2, titanium oxide and TiO 2 were phase components and chemical components, respectively, and in the case of chemical analysis, the lower oxides of titanium were expressed as TiO2, and in the case of X-ray testing of the phase components, the lower oxides of titanium were clearly shown.
When ferrotitanium alloy is produced, ilmenite is used as a main raw material, aluminum metal is used as a reducing agent, light burned magnesia or magnesite is used as a slag former, and ferrotitanium alloy is prepared through aluminothermic reaction under the high temperature condition (generally above 1900 ℃), and the slag and the ferrotitanium alloy are easy to separate due to different specific gravities. After normal cooling time, the slag cover is uncovered, slag and iron are thoroughly separated, no adhesion exists, and the slag and iron mixed melting layer at the bottom sand nest part is 1-3 cm. The main component of the prepared titanium-iron slag is alumina-magnesia-alumina spinel, contains a small amount of metallic titanium and oxides of divalent titanium and tetravalent titanium, can be directly used as corundum-spinel refractory raw materials, realizes the utilization of high added value of the titanium slag, has the finished product yield of 61-69% of ferrotitanium, and is slightly lower than the traditional lime slagging process, but the comprehensive value of the whole process product is superior to that of the traditional lime slagging process.
Compared with the prior art, the invention has the following positive effects:
The refractory material takes ferrotitanium slag as a main material, changes the main component of the ferrotitanium slag by changing the existing slag forming material, fully utilizes the latent heat of slag, directly synthesizes corundum-spinel material, is directly used as a high-grade raw material of the refractory material after being crushed, improves the use value of the ferrotitanium slag, can greatly reduce the production cost of the corundum-spinel material, and has no special equipment requirement in production and simple process. The main phase composition of the prepared corundum-spinel refractory raw material comprises alumina, magnesia-alumina spinel and titanium sesquioxide, and the refractoriness of the material is more than or equal to 1790 ℃; the volume density is 3.35-3.55 g/cm 3.
The method has the characteristics of simple implementation process, high comprehensive cost performance of the whole process product and no special requirement on equipment, and the corundum-spinel refractory raw material prepared by the method is directly used in the refractory material industry, so that the high-efficiency utilization of the titanium iron slag is realized.
Claims (5)
1. A corundum-spinel refractory raw material taking ferrotitanium slag as a main material is characterized in that: the corundum-spinel refractory raw material comprises 72.0～80.0wt% Al2O3、15.0～20.0 wt % TiO2、3.0～8.0 wt %MgO、0～0.5 wt % Fe2O3 and 0-0.7% wt% SiO 2.
2. The corundum-spinel refractory raw material using titanium slag as a main material according to claim 1, characterized in that: the phase composition of the corundum-spinel refractory raw material comprises corundum, magnesia-alumina spinel and titanium oxide.
3. A method for preparing a corundum-spinel refractory material using ilmenite as a main material according to claim 1 or 2, characterized in that the method comprises the following steps:
step one, when slag formation is carried out in the ferrotitanium smelting production process, light burned magnesia or magnesite is used as a slag former;
smelting and deslagging according to a ferrotitanium production process or uncovering a slag cover after cooling, so that slag and iron are thoroughly separated;
and thirdly, crushing the cooled ferrotitanium slag to prepare the granularity meeting the production requirement of the refractory material, thereby obtaining the corundum-spinel refractory material.
4. The method for preparing a corundum-spinel refractory raw material using titanium slag as a main material according to claim 3, characterized by comprising the steps of: the weight percentage of MgO content in the light burned magnesia is more than 85.0%, the weight percentage of MgO content in the magnesite is more than 41.0%, and the granularity is 100 mesh screen blanking.
5. The method for preparing a corundum-spinel refractory raw material using titanium slag as a main material according to claim 3, characterized by comprising the steps of: the addition amount of the light burned magnesia or magnesite is 1-6% of the weight of ferrotitanium smelting ingredients.
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| CN202211603124.XA CN118184369A (en) | 2022-12-14 | 2022-12-14 | Corundum-spinel refractory material taking ferrotitanium slag as main material and preparation method thereof |
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| CN202211603124.XA CN118184369A (en) | 2022-12-14 | 2022-12-14 | Corundum-spinel refractory material taking ferrotitanium slag as main material and preparation method thereof |
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