CN117430436B - Chromium-aluminum-zirconium refractory material for melting layered part of melting separation furnace and preparation method and application thereof - Google Patents
Chromium-aluminum-zirconium refractory material for melting layered part of melting separation furnace and preparation method and application thereof Download PDFInfo
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- CN117430436B CN117430436B CN202311757134.3A CN202311757134A CN117430436B CN 117430436 B CN117430436 B CN 117430436B CN 202311757134 A CN202311757134 A CN 202311757134A CN 117430436 B CN117430436 B CN 117430436B
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- 238000002844 melting Methods 0.000 title claims abstract description 54
- 230000008018 melting Effects 0.000 title claims abstract description 53
- 239000011819 refractory material Substances 0.000 title claims abstract description 48
- -1 Chromium-aluminum-zirconium Chemical compound 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000926 separation method Methods 0.000 title claims description 10
- 239000002245 particle Substances 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 51
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 49
- 239000011029 spinel Substances 0.000 claims abstract description 49
- 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 39
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 36
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 16
- 238000003723 Smelting Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000005496 eutectics Effects 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002893 slag Substances 0.000 abstract description 28
- 230000003628 erosive effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 3
- 230000008719 thickening Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 40
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 24
- 229910052742 iron Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 230000035939 shock Effects 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000004131 Bayer process Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012768 molten material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical class [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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Abstract
The invention discloses a chromium-aluminum-zirconium refractory material for a melting layering part of a melting furnace, and a preparation method and application thereof, and belongs to the technical field of refractory materials. The chromium-aluminum-zirconium refractory material comprises 5-10 parts by weight of aluminum-magnesium spinel particles, 70-80 parts by weight of electric smelting chromium oxide particles, 8-10 parts by weight of remelting particles, 3-5 parts by weight of zirconia micropowder, 5-7 parts by weight of alumina micropowder and 3-5 parts by weight of binding agent. On one hand, the aluminum magnesium spinel used in the invention can absorb erosion components in slag, on the other hand, the generated tiny secondary spinel phase forms a shell on the surface of the material, so that the porosity of an interface is reduced, the slag erosion resistance and permeability of the refractory material are obviously improved, various high-temperature properties of the material are improved, the thickening of the interface is achieved, and the excellent slag resistance using effect is realized.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and particularly relates to a chromium-aluminum-zirconium refractory material for a melting layering part of a melting furnace, and a preparation method and application thereof.
Background
The red mud is waste residue discharged in the alumina production process, and the problems of extremely low utilization rate, huge red mud stacking become worldwide problems due to the reasons of technology, cost and the like. The alkaline and high-salinity red mud waste liquid causes the alkalization of water and soil and pollutes underground water sources, so that the environmental protection pressure is greatly increased, and the sustainable alumina industry in China is severely restrictedDevelopment. However, bayer process red mud contains higher ferric oxide, fe 2 O 3 The content is generally over 30-40%, which can be used as raw material for iron making, and the world is striving for comprehensive utilization method, and the recovery of iron resources from red mud is significant for supplementing iron ore resources in China.
At present, the stable and mature comprehensive utilization technology in China can realize the complete utilization of red mud, namely 'eating, drying and squeezing completely', and adopts a new technological process of coal-based direct reduction sintering, magnetic separation of slag and iron and mother liquor dissolution. The method comprises the steps of adding lignite (carbon, silicon dioxide, aluminum oxide, magnesium oxide and other components) into high-iron red mud which is dissolved and refined by a Bayer process, using lignite (a poor-quality coal and resources which cannot be used for generating electricity) existing in a large amount after coal mine is adopted, adding bentonite as a reducing agent, pressing into balls under high pressure, mineralizing by a rotary hearth furnace, catalyzing and reducing into elemental iron or ferric oxide to form very good balls, adding a small amount of lime and coke powder, melting in a melting furnace, and controlling parameters such as liquid-solid ratio and the like to dissolve clinker in alkali liquor after the melting is carried out in a strong melting mode. The specific gravity of iron is relatively large, molten iron sinks to the bottom of the lower layer, slag rich in a large amount of silicon dioxide floats to the upper layer of the molten iron, slag and molten iron are separated, high-alumina lye and iron-rich residues are obtained, and the upper layer contains iron oxide, aluminum oxide, calcium oxide, magnesium oxide, potassium oxide, sodium oxide and other components and is a main raw material for producing mineral wool. The molten iron at the bottom of the lower layer is discharged through a tap hole to produce high-quality molten iron, and the product can be used as a semi-steel raw material for electric furnace steelmaking. The technology not only realizes the extraction and utilization of metallic iron elements in the Bayer process red mud, but also can realize the comprehensive and comprehensive utilization of the Bayer process red mud.
During melting in a melting furnace, alkaline slag attack is very severe because of the very high alkaline content. In the working condition environment of the lower layer non-iron and non-steel, if the working condition is according to the ironmaking working condition, the furnace lining material is optimally prepared by adding carbon-containing materials into aluminum-silicon series materials; if the working condition of steelmaking is the working condition, the alkaline carbonaceous material is the optimal. The smelting working condition of the red mud is acid and alkali slag erosion, acid and alkali, ultrahigh temperature (1600-1800 ℃), and the temperature change in the smelting process is very severe, and the working conditions of the upper part and the lower part of the whole molten pool are very different: the refractory for melting furnaces has a problem that the development of the melting technology is restricted because the refractory varies greatly, the upper part of the melt is acidic and the lower part of the melt is alkaline. The problems of furnace lining material complete melting, iron tap hole blockage, furnace body reddening and furnace body burning-through in high-temperature smelting, furnace hearth complete melting and damage and the like respectively occur in the prior high-alumina system, magnesium system (magnesia chromium, magnesia spinel, magnesia-alumina spinel), alumina spinel, magnesia-carbon brick, alumina-magnesia-carbon brick, composite material, chrome corundum and the like.
The melting tank of the melting separation furnace is a key harsh part for melting and separating molten materials, the part of the melting tank needs to frequently receive newly input materials, the fluctuation range of the temperature of the molten materials is also large, but the fluctuation range of the temperature of the molten materials is smaller than that of a feed opening; meanwhile, the upper part of the molten bath is high silicon molten bath, namely an acidic environment, and SiO resistance is required 2 The lower part of the acid melt is iron-rich residue and contains a large amount of CaO, mgO, K 2 O、Na 2 O, i.e., alkaline environment, requires alkali resistant component (iron, calcium, magnesium, etc.) materials to attack. Therefore, the lining material of the tank wall is required to have excellent acid resistance, alkali corrosion resistance, ultrahigh temperature resistance, strong slag corrosion resistance, molten iron erosion resistance and penetration resistance, and particularly FeO corrosion resistance in slag. The conventional refractory material is prepared by adding mullite, zirconia and the like, but is not suitable for regulating chemical components and phases of the refractory material of the pool wall, and does not meet the working condition requirements of resisting acid and alkali corrosion and improving thermal shock resistance. Therefore, the research and development of the refractory material applied to the melting and layering part of the melting and separating furnace has important significance for recycling the red mud.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgment or any form of suggestion that this information is prior art that is well known to those of ordinary skill in the art.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a chromium-aluminum-zirconium refractory material for a melting and layering part of a melting and separating furnace, a preparation method and application thereof, wherein the melting and separating tank of the melting and separating furnace is in complex working conditions of acid and alkali, slag erosion, molten iron erosion and the like in the environment when red mud is recycled, and the refractory material in the prior art is not suitable for chemical component regulation and phase regulation of the refractory material of the tank wall and does not meet the working condition requirements of acid and alkali erosion resistance, thermal shock resistance and the like.
The invention provides a chromium-aluminum-zirconium refractory material for a melting and layering part of a melting furnace, which comprises 5-10 parts by weight of aluminum-magnesium spinel particles, 70-80 parts by weight of electric melting chromium oxide particles, 8-10 parts by weight of remelting particles, 3-5 parts by weight of zirconia micropowder, 5-7 parts by weight of alumina micropowder and 3-5 parts by weight of binding agent;
the aluminum magnesium spinel particles are magnesium-rich spinel, and comprise 65 weight percent of Al 2 O 3 And 30wt% MgO.
In some embodiments, the aluminum magnesium spinel has a particle size of 3-1mm.
In some embodiments, the particle size distribution and weight ratio of the electrically fused chromia particles is (5-3 mm): (3-1 mm): (1-0 mm) =1:1:1.5.
In some embodiments, the remelting particles are aluminum-chromium eutectic, in particular, the remelting particles are aluminum-chromium slag remelted at high temperature, and CaO, mgO, fe is removed 2 O 3 、K 2 O、Na 2 O and other impurities to form high-quality aluminium-chromium eutectic. Al in the remelted material particles 2 O 3 And Cr (V) 2 O 3 The total amount of the components is more than or equal to 94 weight percent, and SiO in the remelting particles 2 The content of (2) is less than or equal to 1.0wt%.
In some embodiments, the remelted particles have a particle size distribution and weight ratio of (5-3 mm): (3-1 mm) =1:1.
In some embodiments, the binding agent is an alumina sol.
In some embodiments, the alumina sol is ρ—Al 2 O 3 Micropowder and alpha-Al 2 O 3 Boehmite gel formed by adding water into micro powder, wherein rho-Al 2 O 3 Micro powder and alpha-Al 2 O 3 The granularity of the micro powder is less than 1 mu m.
In some embodiments, the α -Al 2 O 3 Micropowder and the rho-Al 2 O 3 The weight ratio of the micro powder is 1:1.
ρ-Al 2 O 3 Is of an unshaped structure, defective and alpha-Al 2 O 3 The high-activity phase formed in the sintering process, namely the aluminum-chromium eutectic with fine crystalline phase, is formed after mixing and adding water, and has good activity, sintering can be promoted under the medium-low temperature condition, the product is densified under the high-temperature condition, and the product can resist high-temperature acid slag and can resist corrosion of strong alkaline slag.
α-Al 2 O 3 The binding agent can be uniformly distributed on any part of the material along with the full sintering of the material to form ceramic phase combination, so that the initial strength of the material can be improved, the later sintering performance of the material can be improved, and the high-temperature resistant chemical component is relatively high in the high-temperature application state, such as the content of aluminum oxide is improved, so that the high-temperature resistant performance is correspondingly excellent.
The second aspect of the invention provides a method for preparing a chromium-aluminum-zirconium refractory material, comprising the following steps:
s1, uniformly mixing the aluminum magnesium spinel particles, the electric smelting chromium oxide particles and the remelting particles to obtain premixed particles;
s2, uniformly mixing the zirconia micro powder and the alumina micro powder to obtain premixed matrix fine powder;
s3, ageing the materials, pressurizing, forming, drying and sintering to obtain the chromium-aluminum-zirconium refractory material.
In some embodiments, the time for the trapping is 24-72 hours;
and/or the pressure of the pressurization is 600T-1000T;
and/or the drying temperature is 150-180 ℃ and the drying time is 24-48 hours;
and/or, the sintering temperature is 1550-1600 ℃, and the heat preservation is carried out for 16 hours.
The impurities such as calcium, magnesium, iron and the like in a small amount in the material are trapped by the material and the binding agent for a sufficient reaction time, so that the material forms complete chemical bond combination, the plasticity of the material is improved, the molding is convenient, and the normal-temperature physical property and the high-temperature service performance of the material can be improved. Preferably, the time of trapping the materials is adjusted according to different seasons and different temperatures, for example, the time of trapping the materials is shortened properly in summer or when the temperature is higher, and the time of trapping the materials is prolonged properly in winter or when the temperature is lower.
The third aspect of the invention provides an application of the chromium-aluminum-zirconium refractory material or the chromium-aluminum-zirconium refractory material prepared by the preparation method in a melting and layering part of a red mud recovery melting and separating furnace.
The technical principle of the invention is as follows:
according to the working conditions, the magnesia-rich spinel is selected as the medium-sized particles for the pool wall refractory material, and resists erosion and thermal shock resistance of the material, because the magnesia-rich spinel is neutral, the magnesia-rich spinel has good erosion resistance to acidic and alkaline slag, can absorb erosion components in the slag, and contains a large amount of CaO, mgO, fe 2 O 3 Al in the aluminum magnesium spinel in the use process 2 O 3 CaO, mgO, fe in the sum slag 2 O 3 Generating secondary spinel, forming a shell on the surface of the material by the tiny spinel phase, reducing the porosity of an interface, obviously improving the slag erosion resistance and permeability, improving various high-temperature properties of the material, achieving the thickening of the interface and realizing the excellent use effect of slag resistance by slag; the addition of the aluminum magnesium spinel can also remarkably improve the thermal shock resistance of the aluminum chromium material (the conventional refractory material is prepared by adding mullite, zirconia and the like, but is not suitable for the chemical component regulation and phase regulation of the refractory material of the tank wall, and does not meet the working condition requirements of not only resisting acid and alkali corrosion, but also improving the thermal shock resistance).
The addition of the alumina micropowder can generate proper amount of in-situ magnesia-alumina spinel in the matrix, and in the magnesia-alumina spinel structure, strong ionic bonds are formed between Al-O, mg-O, and the strength of electrostatic bonds is equal, so that the structure is firm. Therefore, the saturated structure of the magnesia-alumina spinel crystal has good thermal shock stability, chemical erosion resistance and wear resistance, and can maintain good stability in an oxidizing or reducing atmosphere. Meanwhile, aluminum oxide reacts with electrofused chromium oxide to form a viscous aluminum-chromium solid solution, so that the slag resistance of the product is greatly improved.
The addition of zirconia micropowder is not only beneficial to improving the thermal shock resistance of products, but also ZrO 2 The high-melting-point monocalcium zirconate is generated by the reaction of the high-melting-point monocalcium zirconate and CaO, so that the alkaline medium can be effectively prevented from penetrating into the product, and the spinel is protected from being decomposed.
Compared with the prior art, the invention has the following technical effects:
(1) The magnesium-rich spinel (containing 30wt% of MgO) adopted by the invention is neutral, and has good erosion resistance to both acid and alkaline slag; in addition, the red mud slag contains a large amount of CaO, mgO, fe 2 O 3 Al in the aluminum magnesium spinel in the use process 2 O 3 CaO, mgO, fe in the sum slag 2 O 3 The aluminum-magnesium spinel used in the invention can absorb erosion components in slag on one hand, and on the other hand, the generated tiny secondary spinel phase forms a shell (shown in figure 2) on the surface of the material, so that the slag erosion resistance and permeability of the refractory material are obviously improved, various high-temperature properties of the material are improved, interface thickening is achieved, and excellent slag resistance using effect is realized.
(2) The invention also adds alumina micropowder and zirconia micropowder. The alumina reacts with the electrofused chromium oxide to form a viscous aluminum-chromium solid solution, so that the slag resistance of the product is greatly improved; the addition of zirconia micropowder is not only beneficial to improving the thermal shock resistance of products, but also ZrO 2 The high-melting-point monocalcium zirconate is generated by the reaction of the high-melting-point monocalcium zirconate and CaO, so that the alkaline medium can be effectively prevented from penetrating into the product, and the spinel is protected from being decomposed.
Drawings
FIG. 1 is an SEM image of a refractory material prepared according to example 1 of the present invention;
FIG. 2 is a schematic diagram of the formation of a "shell" on the surface of a material by a secondary spinel phase, where (a) is before the reaction and (b) is after the reaction.
Detailed Description
The technical scheme of the invention is described below through specific embodiments with reference to the accompanying drawings. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
Example 1
The chromium-aluminum-zirconium refractory material for the melting layering part of the melting separation furnace comprises 8 parts by weight of aluminum-magnesium spinel particles, 75 parts by weight of electro-fused chromium oxide particles, 9 parts by weight of remelting particles, 5 parts by weight of zirconia micropowder, 6 parts by weight of alumina micropowder and 4 parts by weight of alumina sol binder.
The aluminum magnesium spinel particles are rich magnesium spinel with a granularity of 3-1mm and comprise 65wt% of Al 2 O 3 And 30wt% MgO.
The particle size distribution and the proportion of the electric smelting chromium oxide particles are (5-3 mm): (3-1 mm): (1-0 mm) =1:1:1.5.
The remelting material particles are aluminum-chromium eutectic, and Al in the remelting material particles 2 O 3 And Cr (V) 2 O 3 The total amount of SiO in the remelted particles was 97wt% 2 The content of (3) is 0.5wt%, and the grain size distribution and the proportion of the remelted material particles are (5-3 mm): (3-1 mm) =1:1.
The preparation method of the alumina sol comprises the following steps: rho-Al with weight ratio of 1:1 2 O 3 Micropowder and alpha-Al 2 O 3 After adding water into the micro powder, stirring uniformly to form boehmite gel, namely alumina sol, wherein the rho-Al 2 O 3 Micro powder and alpha-Al 2 O 3 The granularity of the micro powder is less than 1 mu m.
The preparation method of the chromium-aluminum-zirconium refractory material for the melting layering part of the melting separation furnace comprises the following steps:
s1: uniformly mixing the aluminum magnesium spinel particles, the electric smelting chromium oxide particles and the remelting particles to obtain premixed particles;
s2: uniformly mixing the zirconia micropowder and the alumina micropowder to obtain premixed matrix fine powder;
s3: the material is trapped for 48 hours;
s4: pressurizing and forming, wherein the pressurizing pressure is 800T;
s5: drying at 165 ℃ for 36 hours;
s6: and (3) sintering at 1550 ℃, preserving heat for 16 hours, and cooling to obtain the chromium-aluminum-zirconium refractory material.
The prepared chromium-aluminum-zirconium refractory material achieves the following indexes through tests:
as a result of SEM scanning of the above-mentioned chromium-aluminum-zirconium refractory, as shown in fig. 1, it can be seen that a shell (dotted line area in fig. 1) is formed on the surface of the material by the fine secondary spinel phase, and the outside of the aluminum-magnesium spinel (MA, solid line area in fig. 1) is coated, and the formation principle is shown in fig. 2, wherein (a) is before the reaction and (b) is after the reaction.
The chromium-aluminum-zirconium refractory material is applied to the melting and layering part of the melting and separating furnace and is used for recycling red mud, and after the red mud is used for 10 times, the melting and layering part of the melting and separating furnace is not burnt through and is not damaged.
Example 2
The chromium-aluminum-zirconium refractory material for the melting layering part of the melting separation furnace comprises 5 parts by weight of aluminum-magnesium spinel particles, 70 parts by weight of electro-fused chromium oxide particles, 8 parts by weight of remelting particles, 3 parts by weight of zirconia micropowder, 5 parts by weight of alumina micropowder and 3 parts by weight of alumina sol binder.
The aluminum magnesium spinel particles are rich magnesium spinel with a granularity of 3-1mm and comprise 65wt% of Al 2 O 3 And 30wt% MgO.
The particle size distribution and the proportion of the electric smelting chromium oxide particles are (5-3 mm): (3-1 mm): (1-0 mm) =1:1:1.5.
The remelting material particles are aluminum-chromium eutectic, and Al in the remelting material particles 2 O 3 And Cr (V) 2 O 3 The total amount of SiO in the remelted particles was 96wt% 2 The content of (3) is 0.6wt%, and the grain size distribution and the proportion of the remelted material particles are (5-3 mm): (3-1 mm) =1:1.
The preparation method of the alumina sol comprises the following steps: rho-Al with weight ratio of 1:1 2 O 3 Micropowder and alpha-Al 2 O 3 After adding water into the micro powder, stirring uniformly to form boehmite gel, namely alumina sol, wherein the rho-Al 2 O 3 Micro powder and alpha-Al 2 O 3 The granularity of the micro powder is less than 1 mu m.
The preparation method of the chromium-aluminum-zirconium refractory material for the melting layering part of the melting separation furnace comprises the following steps:
s1: uniformly mixing the aluminum magnesium spinel particles, the electric smelting chromium oxide particles and the remelting particles to obtain premixed particles;
s2: uniformly mixing the zirconia micropowder and the alumina micropowder to obtain premixed matrix fine powder;
s3: the material is trapped for 24 hours;
s4: pressurizing and forming, wherein the pressurizing pressure is 600T;
s5: drying at 180 ℃ for 24 hours;
s6: and (3) sintering at 1550 ℃, preserving heat for 16 hours, and cooling to obtain the chromium-aluminum-zirconium refractory material.
The obtained chromium-aluminum-zirconium refractory material is detected and applied, and the result is consistent with the embodiment and is not repeated here.
The prepared chromium-aluminum-zirconium refractory material achieves the following indexes through tests:
example 3
The chromium-aluminum-zirconium refractory material for the melting layering part of the melting separation furnace comprises 10 parts by weight of aluminum-magnesium spinel particles, 80 parts by weight of electro-fused chromium oxide particles, 10 parts by weight of remelting particles, 5 parts by weight of zirconia micropowder, 7 parts by weight of alumina micropowder and 5 parts by weight of alumina sol binder.
The aluminum magnesium spinel particles are rich magnesium spinel with a granularity of 3-1mm and comprise 65wt% of Al 2 O 3 And 30wt% MgO.
The particle size distribution and the proportion of the electric smelting chromium oxide particles are (5-3 mm): (3-1 mm): (1-0 mm) =1:1:1.5.
The remelting material particles are aluminum-chromium eutectic, and Al in the remelting material particles 2 O 3 And Cr (V) 2 O 3 The total amount of SiO in the remelted particles was 97wt% 2 The content of the remelted material particles is 0.7wt%, and the grain size distribution and the proportion of the remelted material particles are (5-3 mm): (3-1 mm) =1:1.
The preparation method of the alumina sol comprises the following steps: rho-Al with weight ratio of 1:1 2 O 3 Micropowder and alpha-Al 2 O 3 After adding water into the micro powder, stirring uniformly to form boehmite gel, namely alumina sol, wherein the rho-Al 2 O 3 Micro powder and alpha-Al 2 O 3 The granularity of the micro powder is less than 1 mu m.
The preparation method of the chromium-aluminum-zirconium refractory material for the melting layering part of the melting separation furnace comprises the following steps:
s1: uniformly mixing the aluminum magnesium spinel particles, the electric smelting chromium oxide particles and the remelting particles to obtain premixed particles;
s2: uniformly mixing the zirconia micropowder and the alumina micropowder to obtain premixed matrix fine powder;
s3: the time for trapping the materials is 72 hours;
s4: pressurizing and forming, wherein the pressurizing pressure is 1000T;
s5: drying at 150 ℃ for 48 hours;
s6: and (3) sintering at 1600 ℃, preserving heat for 16 hours, and cooling to obtain the chromium-aluminum-zirconium refractory material.
The prepared chromium-aluminum-zirconium refractory material achieves the following indexes through tests:
the obtained chromium-aluminum-zirconium refractory material is detected and applied, and the result is consistent with the embodiment and is not repeated here.
Comparative example 1
This comparative example differs from example 1 in that the aluminum magnesium spinel is an aluminum rich spinel comprising 76% by weight of Al 2 O 3 And 24% by weight of MgO, the other matters being the same as in example 1.
The performance parameters of the refractory materials prepared in this comparative example are shown in the following table:
comparative example 2
This comparative example differs from example 1 in that a 1:1 combination of phosphoric acid and aluminum dihydrogen phosphate was used in place of the alumina sol binder of example 1, the total amount of phosphoric acid and aluminum dihydrogen phosphate being consistent with the parts by weight of the alumina gel of example 1.
The performance parameters of the refractory materials prepared in this comparative example are shown in the following table:
comparative example 3
This comparative example was different from example 1 in that no zirconia fine powder was added, and the other was the same as example 1.
The performance parameters of the refractory materials prepared in this comparative example are shown in the following table:
comparative example 4
This comparative example was different from example 1 in that no alumina fine powder was added, and the other was the same as in example 1.
The performance parameters of the refractory materials prepared in this comparative example are shown in the following table:
as can be seen, the refractory materials prepared in comparative examples 1-4 all have different degrees of degradation in performance parameters compared to the refractory material prepared in example 1.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. The chromium-aluminum-zirconium refractory material for the melting layering part of the melting separation furnace is characterized in that the raw materials of the chromium-aluminum-zirconium refractory material comprise 5-10 parts by weight of aluminum-magnesium spinel particles, 70-80 parts by weight of electro-melting chromium oxide particles, 8-10 parts by weight of remelting material particles, 3-5 parts by weight of zirconia micropowder, 5-7 parts by weight of alumina micropowder and 3-5 parts by weight of binding agent;
the aluminum magnesium spinel particles are magnesium-rich spinel, and comprise 65 weight percent of Al 2 O 3 And 30wt% MgO;
the remeltingThe material particles are aluminium-chromium eutectic, and Al in the remelted material particles 2 O 3 And Cr (V) 2 O 3 The total amount of (2) is more than or equal to 94wt%;
the binding agent is alumina sol, and the alumina sol is rho-Al 2 O 3 Micropowder and alpha-Al 2 O 3 Boehmite gel formed by adding water into micro powder, wherein rho-Al 2 O 3 Micro powder and alpha-Al 2 O 3 The granularity of the micro powder is less than 1 mu m.
2. The chromia-alumina-zirconia refractory as claimed in claim 1, wherein said aluminium-magnesium spinel has a particle size of 3-1mm.
3. The chromia-aluminozirconium refractory according to claim 1, wherein the particle size distribution and weight ratio of the electrofused chromia particles is (5-3 mm): (3-1 mm): (1-0 mm) =1:1:1.5.
4. The chromia-alumino-zirconia refractory according to claim 1, wherein SiO in said remelted particles 2 The content of the remelting material particles is less than or equal to 1.0 weight percent, and the grain size distribution and the weight ratio of the remelting material particles are (5-3 mm): (3-1 mm) =1:1.
5. The chromiumzirconia refractory of claim 1, wherein said α -Al 2 O 3 Micropowder and the rho-Al 2 O 3 The weight ratio of the micro powder is 1:1.
6. The method for producing a chromium-aluminum-zirconium refractory according to claim 1, comprising:
s1, uniformly mixing the aluminum magnesium spinel particles, the electric smelting chromium oxide particles and the remelting particles to obtain premixed particles;
s2, uniformly mixing the zirconia micro powder and the alumina micro powder to obtain premixed matrix fine powder;
s3, ageing the materials, pressurizing, forming, drying and sintering to obtain the chromium-aluminum-zirconium refractory material.
7. The method of claim 6, wherein the time for trapping the material is 24-72 hours;
and/or the pressure of the pressurization is 600T-1000T;
and/or the drying temperature is 150-180 ℃ and the drying time is 24-48 hours;
and/or, the sintering temperature is 1550-1600 ℃, and the heat preservation is carried out for 16 hours.
8. The use of the chromium-aluminum-zirconium refractory according to any one of claims 1 to 5 or prepared by the preparation method according to any one of claims 6 to 7 in a red mud recovery melting and separating furnace at a melting and layering position.
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| DE2350662A1 (en) * | 1973-10-09 | 1975-04-17 | Pickford Holland Co Ltd | Chrome-magnesite refractory brick compsn - having improved properties |
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| CN116332635A (en) * | 2023-04-04 | 2023-06-27 | 中钢洛耐科技股份有限公司 | Electric smelting zirconium magnesium chromium spinel raw material and preparation method thereof |
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