CN102219535B - Recombined magnesia-alumina spinel brick with properties of nodulation and blockage prevention and high corrosion resistance, and production technology thereof - Google Patents
Recombined magnesia-alumina spinel brick with properties of nodulation and blockage prevention and high corrosion resistance, and production technology thereof Download PDFInfo
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- CN102219535B CN102219535B CN201110108992.6A CN201110108992A CN102219535B CN 102219535 B CN102219535 B CN 102219535B CN 201110108992 A CN201110108992 A CN 201110108992A CN 102219535 B CN102219535 B CN 102219535B
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 90
- 239000011029 spinel Substances 0.000 title claims abstract description 90
- 239000011449 brick Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000005516 engineering process Methods 0.000 title abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title abstract 18
- 230000007797 corrosion Effects 0.000 title abstract 2
- 238000005260 corrosion Methods 0.000 title abstract 2
- 230000024121 nodulation Effects 0.000 title abstract 2
- 230000002265 prevention Effects 0.000 title abstract 2
- 239000004576 sand Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000010419 fine particle Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000003265 pulping liquor Substances 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract 12
- 239000011230 binding agent Substances 0.000 claims abstract 5
- 239000011362 coarse particle Substances 0.000 claims abstract 2
- 238000001238 wet grinding Methods 0.000 claims abstract 2
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 18
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910020068 MgAl Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 241001131796 Botaurus stellaris Species 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 3
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 235000007164 Oryza sativa Nutrition 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000012267 brine Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000002706 hydrostatic effect Effects 0.000 abstract 1
- 235000009566 rice Nutrition 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 26
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 20
- 239000000292 calcium oxide Substances 0.000 description 18
- 239000003595 mist Substances 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000446 fuel Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000007767 bonding agent Substances 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001095 magnesium carbonate Substances 0.000 description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 6
- 235000014380 magnesium carbonate Nutrition 0.000 description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 241001504664 Crossocheilus latius Species 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 230000005496 eutectics Effects 0.000 description 5
- 239000005329 float glass Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000011194 food seasoning agent Nutrition 0.000 description 4
- 239000002006 petroleum coke Substances 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- -1 magnesium aluminate Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000010922 glass waste Substances 0.000 description 1
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a recombined magnesia-alumina spinel brick with properties of nodulation and blockage prevention and high corrosion resistance, and a production technology thereof. A formula of the recombined magnesia-alumina spinel brick comprises 30 to 40 wt% of fused magnesia-alumina spinel sand with a granularity of 5 to 3 millimeters, 20 to 35 wt% of fused magnesia-alumina spinel sand with a granularity of 4 to 2 millimeters, 5 to 15 wt% of fused magnesia-alumina spinel sand with a granularity of 1 to 0 millimeters, 10 to 15 wt% of fused magnesia-alumina spinel sand with a granularity of 150 to 200 meshes, 5 to 10 wt% of fused magnesia-alumina spinel sand with a granularity of 250 meshes, 1 to 3 wt% of ZrO2 with a granularity of 250 meshes, 1 to 2 wt% of Fe2O3 with a granularity of 250 meshes, and 0 to 1 wt% of CaO with a granularity of 250 meshes. Chemical compositions of the magnesia-alumina spinel brick comprises 26 to 40 wt% of MgO, 55 to 68 wt% of Al2O3, 1.0 to 3.0 wt% of ZrO2, 1.0 to 3.0 wt% of Fe2O3, and 0 to 2.0 wt% of CaO. The production technology of the magnesia-alumina spinel brick comprises the following steps of 1), carrying out a pretreatment on magnesia and alumina, carrying out a synthesis of magnesia-alumina spinel sand, wherein the magnesia-alumina spinel sand contains 26 to 40 wt% of MgO and 55 to 70 wt% of Al2O3, smashing the synthetized magnesia-alumina spinel sand into coarse, medium and fine particles respectively with a granularity of 5 to 3 millimeters, a granularity of 4 to 2 millimeters and a granularity of 1 to 0 millimeters and powder respectively with a granularity of 180 meshes and a granularity of 250 meshes, 2), mixing orderly the coarse particles, medium particles, a binder, the magnesia-alumina spinel powder with a granularity of 150 to 200 meshes, the magnesia-alumina spinel powder with a granularity of 250 meshes, and ZrO2, Fe2O3 and CaO powder according to the formula, and carrying wet milling for 8 to 12 minutes, wherein the binder accounts for 1.0 to 1.8 wt% of the mixed material and is a mixed liquor of spent pulping liquor, brine and polycarboxylic acids, 3), compressing the mixed material obtained from the step 2 into required shapes through multiple devices of a friction press, a Sandes brick machine, a Rice brick machine, a hydrostatic press, etc., and roasting at a temperature of 80 to 160 DEG C for 24 to 72 hours, and 4), heating dry green bodies obtained from the step 3 at a temperature of 1560 to 1710 DEG C for 3 to 5 hours to obtain finished products.
Description
Technical field
The present invention relates to a kind of prepare have high anti-erosion, the blocking of anti-dross again in conjunction with Mg-Al spinel brick and production technique thereof, belong to the technical field of refractory materials of ceramic.This has high resistance to fouling in conjunction with Mg-Al spinel brick again, heat-shock resistance, anti-glass fly material adhesion, anti-dross, nonclogging excellent properties, be applicable to large-scale float glass furnace regenerator lattice, especially be applicable to the glass furnace of cheap fuel, as the glass furnace using coal tar, refinery coke to be fuel, total oxygen/large arch of oxygen-enriched combusting glass furnace.
background technology
Glass industry is important base mateiral industry, closely related with the national economic development.China is glass production state the biggest in the world, and in the end of the year 2009, sheet glass output has accounted for global output more than 40%.Although the output of China's glass occupies first place in the world, but also there is a big difference for glass industry and advanced international standard, main manifestations is that energy consumption remains high, the average hear rate of China's float glass is lower than 7800 kilojoule per kilogram glass metals, higher by 20% than external mean level (ML) (6500 kilojoule per kilogram glass metal), level of emulating the advanced is high by 32%, higher by 53% than best level (5100 kilojoule per kilogram glass metal).In recent years, along with the price of oil, coal, electricity is all rising violently, glass production cost raises increasingly, and energy consumption has accounted for about 50% of float glass cost, brings huge pressure to glass enterprise.Therefore, energy utilization and consumption are depended in the competition in glass market.
For reducing fuel consumption, alleviate the pressure of price of oil going up sky-high, glass enterprise attempts using the refinery coke of heavy oil and coal oil mixture, heavy oil and petroleum coke mixtures, cheapness as fuel.Although use cheap refinery coke to lower energy cost more than 10% for fuel, in the waste gas after petroleum coke combustion and ash content, contain SO
2, P
2o
5, V
2o
5, during the arrival regenerator of these mixtures, become the liquid-solid pureed mixture that viscosity is higher, be bonded in oil gun, cause the muddy length of flame, and often cause oil gun to block and temperature fluctuation; The material of thickness is also bonded on regenerator lattice, make glass fly expect in CaO, Al
2o
3, Na
2o, B
2o
3stick in refractory materials, the foreign material of these adhesions accelerate the erosion to refractory materials.As a result, boning continuously, causing regenerator and the large-area obstruction of checker, checker brick to be subject to strong erosion appears in regenerator within shorter duration of service, distortion, the fault until structure spalling, checker cave in etc.In order to adapt to the negative impact that glass furnace brings to refractory materials for fuel with the refinery coke of cheapness, preparation must be studied and there is anti-erosion, anti-thermal shock, anti, anti-dross, nonclogging novel refractory to substitute current magnesite refractory of being on active service.
The present invention is based on the excellent high-temperature behavior of magnesium-aluminium spinel, in magnesium-aluminium spinel structure, be all stronger ionic linkage, and ionic bond intensity is equal between Al-O, Mg-O, sound construction.Therefore, the saturated structures of magnesium-aluminium spinel crystal has good thermal shock resistance energy, chemistry-resistant characteristic and wear resisting property, can keep good stability in oxidation or reducing atmosphere.Have very excellent anti-petroleum coke combustion waste gas to corrode, anti-glass flies adhesion and the erosion of material.But when synthetic MgAl spinal, meeting is with the volumetric expansion of 5-8%, and its recrystallize ability, is difficult to the magnesium aluminate spinel product of synthesis of densified.The present invention is exactly by adding ZrO
2, Fe
2o
3, CaO preparation can form fatal magnesium aluminate spinel product.ZrO
2tiny crack can be generated in refractory brick, improve heat-shock resistance; ZrO
2can silicate phase be isolated, make it to reduce soaking MgO, improve resistance to fouling; ZrO
2brilliant particle plays pinning effect, decreases the high temperature creep slippage of material, improves the high temperature fracture resistance of material.Add Fe
2o
3produce MF spinel, it admittedly melts and form pattern structure in periclasite and magnesium-aluminium spinel lattice, promote the densified sintering product of spinel brick.
summary of the invention
The object of the invention is to research one prepare there is high anti-erosion, the blocking of anti-dross again in conjunction with Mg-Al spinel brick and production technique thereof, what the present invention was obtained has high thermal resistance in conjunction with Mg-Al spinel brick again, the complex phase spinel combination rate generated is high, material is fine and close, show good hot strength, folding strength, alkali erosiveness, heat-shock resistance, anti-glass flies to expect adhesion, anti-dross, the excellent properties not block etc., the flue gas of resistance to refinery coke and ash attack, anti-glass waste adhesion and alkali corrode, do not block regenerator, extend regenerator material lifetime, be applicable to the high temperature melting furnaces of high alkalinity environment, as the checker brick of glass melter regenerator, spool tile and dividing of cement kiln ungird, be particularly useful for the cheap and impure more refinery coke glass melter regenerator as fuel, and total oxygen/large arch of oxygen-enriched combusting glass furnace etc.
Not easily form the defect of dense product to change magnesium-aluminium spinel, the present invention adds additive and burns agent aid ZrO
2, CaO and Fe
2o
3.Utilize the zirconic characteristic be present in spinel: ZrO
2tiny crack can be generated in refractory brick, improve heat-shock resistance; ZrO
2isolated silicate phase, what make it to reduce to spinel and periclasite is wetting, improves resistance to fouling; Cracked ZrO
2absorb CaO, SiO in volatilization liquid phase
2to put crystalline distribution, improve the sintering character of magnesite refractory; ZrO
2brilliant particle plays pinning effect, decreases the high temperature creep slippage of material, improves the high temperature fracture resistance of material.In addition, in magnesium-aluminium spinel, a small amount of Fe is added
2o
3during composition, MF spinel can be formed, and admittedly melt in periclasite lattice, pattern structure crystal formation with magnalium.The solubility with temperature of MF spinel in magnesium-aluminium spinel changes and changes, temperature raises solubleness and strengthens, when the temperature decreases then there is more weak anisotropic dendritic crystal and particulate state inclusion precipitating in magnesium-aluminium spinel particle surface and cleavage crack, the change of the solubility with temperature fluctuation of MF spinel contributes to activating lattice, be conducive to promoting spinel and the growth of periclasite crystal and the densified sintering product of goods, this is that the sample cold crushing strength of iron-containing additive is high, void content is low, the major reason that volume density is large, also be the principle that the present invention adds additive and sintering agent.Bonding be two media pass through infiltrate space mutually adsorb the process causing adhesion with phase mutual diffusion.Generally be bonded with the modes such as physical mechanical occlusion, absorption, diffusion.Due to the unreactiveness of electric melting magnesium aluminum spinel, glass flies to expect and spinel is extremely difficult forms the absorption and the diffusion that are less than 5A, is difficult to be formed the stable cohesive body with intensity, therefore has anti and block effect.
By technique of the present invention, add ZrO
2, CaO, Fe
2o
3what additive was obtained has resistance to fouling, heat-shock resistance, wearability in conjunction with Mg-Al spinel brick again, effectively can prevent the V in petroleum coke combustion waste gas and ash content
2o
5, P
2o
5, SO
2adhesion and erosion, prevent glass fly expect CaO, Al
2o
3, Na
2o, B
2o
3adhesion and erosion, being applicable to the regenerator lattice of large-scale float glass furnace, particularly using cheap oil burnt is the regenerator chamber of glass kiln checker of fuel, large-scale float glass furnace regenerator and the checker desirable fire-retardant material of to be a new generation with refinery coke be fuel.In addition, because it has high alkali resistance aggressiveness and heat-shock resistance, be also suitable for the positions such as the large arch of glass furnace of total oxygen/oxygen-enriched combusting.
Technical scheme of the present invention is as follows:
1) in order to improve resistance to fouling, aggregate adopts large grain size magnesium-aluminium spinel sand, and its large grain size particle crystal boundary is few, compact structure, and resistance to fouling is strong;
2) ZrO is mixed in matrix
2, in refractory brick, form tiny crack that can be toughness reinforcing, improve the heat-shock resistance of material;
3) add calcium oxide, ferric oxide micro mist as sintering aid, acceleration of sintering, reduce the apparent porosity of material, improve resistance to fouling, sintering agent can reduce sintering temperature simultaneously, reduces production energy consumption;
4) in bonding agent spent pulping liquor, mix tensio-active agent (sulphonated naphtalene formaldehyde polymkeric substance, poly carboxylic acid etc.), reduce shaping required pressure, by electrically charged for the few particle institute repulsion when punching press, raising formability.
Specific embodiment of the present invention is:
1) Material synthesis and fragmentation.Electric smelting synthetic MgAl spinal raw material, containing Al in the spinel of synthesis
2o
355-70wt%, MgO 30-40wt%, the granularity be then broken into is respectively: 5-3mm, 4-2mm, 1-0mm, 150-200 order, 250 orders.
2) prepare burden.Employing granularity is the electric melting magnesium aluminum spinel sand 30-40wt% of 5-3mm, granularity is the electric melting magnesium aluminum spinel sand 20-35wt% of 4-2mm, granularity is the electric melting magnesium aluminum spinel sand 5-15wt% of 1-0mm, granularity 150-200 object spinel sand 10-15wt%, granularity 250 object spinel sand 5-10wt%, granularity 250 object ZrO
21-3wt%, granularity 250 object Fe
2o
31-2wt%, 250 object CaO 0-1wt%.
3) batch mixing.First add macrobead, then add the bonding agent mixed up, bonding agent add-on is 1.0-1.8wt%.Then fine particle, fine powder, micro mist, additive and sintering agent ZrO is added successively
2, Fe
2o
3, CaO.The bonding agent of modulation is spent pulping liquor, bittern and poly carboxylic acid mixed solution.Powerful batch mixing, wet stone roller 8-12 minute.
4) be shaped.Compound is pressed into required shape, and this plurality of devices such as brick pressing machine, hydropress of the available friction press that is shaped, Sang De brick pressing machine, Lay is shaping.
5) dry.Be 80-160 DEG C of dry kiln inside holding 24-72h in temperature.
6) burn till.Dried base substrate is burnt till in 1560 DEG C-1710 DEG C insulation 3-5h.
After making is magnesium-aluminium spinel, magnesium zirconium eutectic, magnesium iron and magnesium-aluminium spinel body, calcium aluminate in conjunction with Mg-Al spinel brick principal crystalline phase again, and main chemical compositions has: content of MgO 26-40wt%, Al
2o
3content 55-68wt%, ZrO
2content 1.0-3.0wt%, Fe
2o
3content 1.0-3.0wt%, CaO content 0-2.0wt%.Table 1 lists its performance.
The magnesium zirconia block performance that table 1 is invented
Embodiment
Embodiment one
Raw material employing granularity is the electric melting magnesium aluminum spinel sand 40wt% of 5-3mm, granularity is the electric melting magnesium aluminum spinel sand 20wt% of 4-2mm, granularity is the electric molten magnesite rate spinel sand 10wt% of 1-0mm, granularity 150 object electric melting magnesium aluminum spinel sand 10wt%, the electric melting magnesium aluminum spinel sand fine powder 15wt% of granularity 250, granularity 250 object desiliconization zirconium white micro mist 2wt%, granularity 250 object ferric oxide micro mist 2wt%, granularity 250 object calcium oxide micro mist 1wt%.Above raw material is first added macrobead, then adds the bonding agent 1.6wt% mixed up, then add fine particle, fine powder, micro mist successively, wet stone roller 8 minutes.Adopt hydraulic pressure 300MPa pressure, keep the 60s time to be shaped.After seasoning 48h, push 120 DEG C of dry kiln inside holding 48h.Burn till in 1560 DEG C of insulation 4h.
After making is magnesium-aluminium spinel, magnesium zirconium eutectic, calcium aluminoferrite in conjunction with Mg-Al spinel brick principal crystalline phase again, and main chemical compositions has: content of MgO 26.8wt%, Al
2o
3content 65.8wt% etc., ZrO
2content 1.98wt%, Fe
2o
3content 2.58wt%, CaO content 1.87wt%, SiO
2content 0.83wt%.Its performance index are as table 2:
The magnesium of table 2 example one spinel brick performance
Embodiment two
Raw material employing granularity is the electric melting magnesium aluminum spinel sand 30wt% of 5-3mm, granularity is the electric melting magnesium aluminum spinel sand 30wt% of 4-2mm, granularity is the electric molten magnesite rate spinel sand 15wt% of 1-0mm, granularity 150 object electric melting magnesium aluminum spinel sand 10wt%, the electric melting magnesium aluminum spinel sand fine powder 10wt% of granularity 250, granularity 250 object desiliconization zirconium white micro mist 3wt%, granularity 250 object ferric oxide micro mist 1wt%, granularity 250 object calcium oxide micro mist 1wt%.Above raw material is first added macrobead, then adds the bonding agent 1.3wt% mixed up, then add fine particle, fine powder, micro mist successively, wet stone roller 10 minutes.Adopt hydraulic pressure 400MPa pressure, keep the 60s time to be shaped.After seasoning 24h, push 160 DEG C of dry kiln inside holding 48h.Burn till in 1710 DEG C of insulation 5h.
After making is magnesium-aluminium spinel, magnesium zirconium eutectic, calcium aluminoferrite in conjunction with Mg-Al spinel brick principal crystalline phase again, and main chemical compositions has: content of MgO 37.4wt%, Al
2o
3content 56.3wt% etc., ZrO
2content 3.00wt%, Fe
2o
3content 1.16wt%, CaO content 1.57wt%, SiO
2content 0.52wt%.Its performance index are as table 3:
The Mg-Al spinel brick performance of table 3 example two
Embodiment three
Raw material employing granularity is the electric melting magnesium aluminum spinel sand 35wt% of 5-3mm, granularity is the electric melting magnesium aluminum spinel sand 25wt% of 4-2mm, granularity is the electric molten magnesite rate spinel sand 8wt% of 1-0mm, granularity 150 object electric melting magnesium aluminum spinel sand 15wt%, the electric melting magnesium aluminum spinel sand fine powder 14wt% of granularity 250, granularity 250 object desiliconization zirconium white micro mist 1wt%, granularity 250 object ferric oxide micro mist 1wt%, granularity 250 object calcium oxide micro mist 1wt%.Above raw material is first added macrobead, then adds the bonding agent 1.5wt% mixed up, then add fine particle, fine powder, micro mist successively, wet stone roller 12 minutes.Employing friction press is shaped.After seasoning 24h, push 110 DEG C of dry kiln inside holding 48h.Burn till in 1640 DEG C of insulations 4.
After making is magnesium-aluminium spinel, magnesium zirconium eutectic, calcium aluminoferrite in conjunction with Mg-Al spinel brick principal crystalline phase again, and main chemical compositions has: content of MgO 32.5wt%, Al
2o
3content 62.7wt% etc., ZrO
2content 1.01wt%, Fe
2o
3content 1.36wt%, CaO content 1.44wt%, SiO
2content 0.72wt%.Its performance index are as table 4:
The Mg-Al spinel brick performance of table 4 example three
Embodiment four
Raw material employing granularity is the electric melting magnesium aluminum spinel sand 30wt% of 5-3mm, granularity is the electric melting magnesium aluminum spinel sand 35wt% of 4-2mm, granularity is the electric molten magnesite rate spinel sand 10wt% of 1-0mm, granularity 150 object electric melting magnesium aluminum spinel sand 10wt%, the electric melting magnesium aluminum spinel sand fine powder 11wt% of granularity 250, granularity 250 object desiliconization zirconium white micro mist 2wt%, granularity 250 object ferric oxide micro mist 2wt%, granularity 250 object calcium oxide micro mist 0wt%.Above raw material is first added macrobead, then adds the bonding agent 1.5wt% mixed up, then add fine particle, fine powder, micro mist successively, wet stone roller 12 minutes.Sang De brick pressing machine is adopted to be shaped.After seasoning 48h, push 110 DEG C of dry kiln inside holding 48h.Burn till in 1600 DEG C of insulation 4h.
After making is magnesium-aluminium spinel, magnesium zirconium eutectic, calcium aluminoferrite in conjunction with Mg-Al spinel brick principal crystalline phase again, and main chemical compositions has: content of MgO 32.6wt%, Al
2o
3content 61.2wt% etc., ZrO
2content 2.11wt%, Fe
2o
3content 2.52wt%, CaO content 0.67wt%, SiO
2content 0.66wt%.Its performance index are as table 5:
The Mg-Al spinel brick performance of table 5 example four
Claims (2)
1. have high resistance to fouling, anti-dross blocking again in conjunction with a Mg-Al spinel brick, it is characterized in that: the formula of described Mg-Al spinel brick is:
The main chemical compositions of above-mentioned Mg-Al spinel brick is: content of MgO 26-40wt%, Al
2o
3content 55-68wt%, ZrO
2content 1-3.0wt%, Fe
2o
3content 1.0-3.0wt%, CaO content 0-2.0wt%.
2. produce a production technique for Mg-Al spinel brick described in claim 1, it is characterized by:
1) pre-treatment is carried out to magnesia and aluminum oxide, adopt electric smelting method synthetic MgAl spinal sand, containing MgO 30-40wt%, Al in synthetic MgAl spinal raw material
2o
355-70wt%;
2) synthetic MgAl spinal is broken into carse, medium and small particulate material and 180 orders, the 250 object powders of 5-3mm, 4-2mm, 1-0mm, according to proportioning raw materials according to following order by coarse particles material, middle particulate material, binding agent, fine particle material, 150-200 order magnesium-aluminium spinel powder, 250 object magnesium aluminium spinel powders, ZrO
2, Fe
2o
3, the mixing of CaO powder, then carry out wet grinding 8-12 minute, described binding agent is spent pulping liquor, bittern and poly carboxylic acid mixed solution, and the add-on of binding agent is 1.0-1.8wt%;
3) above-mentioned compound is pressed into required shape, available friction press, hydropress plurality of devices are shaping, at 80-160 DEG C of baking 24-72h;
4) green compact after drying are incubated 3-5h and burn till at 1560-1710 DEG C.
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| CN102731125A (en) * | 2012-07-25 | 2012-10-17 | 大石桥市东兴耐火材料有限公司 | Production process of modified electric smelting magnalium spinel |
| CN102924095B (en) * | 2012-08-08 | 2014-06-11 | 辽宁青花耐火材料股份有限公司 | Magnesium-zirconium-aluminum bricks used in vacuum degassing furnace, and preparation method thereof |
| CN103396127B (en) * | 2013-07-24 | 2015-01-28 | 东北大学 | Aluminum magnesium calcium fire-resistant clinker and preparation method thereof |
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| CN107759214A (en) * | 2017-12-02 | 2018-03-06 | 芜湖乾凯材料科技有限公司 | A kind of high thermal shock resistance magnesia-spinel brick and preparation method thereof |
| CN107935562B (en) * | 2017-12-02 | 2020-09-25 | 山东鲁桥新材料股份有限公司 | Chromium-free brick for high-temperature zone of dry-process cement kiln and preparation method thereof |
| CN108285349A (en) * | 2017-12-21 | 2018-07-17 | 江苏诺明高温材料股份有限公司 | A method of preparing cement kiln clinkering zone refractory material with fine iron breeze |
| CN112250449A (en) * | 2020-09-15 | 2021-01-22 | 辽宁东和新材料股份有限公司 | Synthetic method of light-burned magnesia-alumina spinel intermediate |
| CN114133227A (en) * | 2021-12-08 | 2022-03-04 | 湖南仁海科技材料发展有限公司 | Long-life wire laying plate and preparation method thereof |
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| CN101580402A (en) * | 2009-06-22 | 2009-11-18 | 河北理工大学 | Magnesia alumina spinel-zirconia-ferric oxide composite material and preparation method thereof |
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