CN1827555A - Non-oxide composite refractory materials for molten iron chute - Google Patents
Non-oxide composite refractory materials for molten iron chute Download PDFInfo
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- CN1827555A CN1827555A CN 200510024099 CN200510024099A CN1827555A CN 1827555 A CN1827555 A CN 1827555A CN 200510024099 CN200510024099 CN 200510024099 CN 200510024099 A CN200510024099 A CN 200510024099A CN 1827555 A CN1827555 A CN 1827555A
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Abstract
The invention relates to a technology for preparation of refractory material, and especially to a composite refractory of non-oxidized substance used in a hot-metal launder of consecutive pre-processing. The composite refractory of non-oxidized substance used in a hot-metal launder is characterized in that it contains (wt %) 50-70 % of corundum material, 15-30 % of silicon carbide, 3-10 % of silicon nitride, 3-10 % of silicon nitride tiny powder, 1-5 % of charcoal material, 1-3 % of silicon anti-oxidization agent, 6-15 % of additional silicasol astringent, and a few additives containing anti-knock agent and dispersing agent with 0.15-1.5 % by wt. The refractory material of the said invention can resist the erosion of the hot-metal and the molten ash and is of strong erosion ability, uniform and high-integrity structure, high intensity at a medium-high-temperature, strong stability of resistance to heat shocks and of volume of material, and strong resistance to oxidation, so it adapts to the process requirement of the desired hot-metal launder of consecutive pre-processing.
Description
(1) technical field
The present invention relates to the refractory materials manufacturing technology, relate in particular to the non-oxide composite refractory materials for molten iron chute in the continuous pre-treatment of molten iron.
(2) background technology
In smelting iron and steel technology, the hot metal pretreatment technology is generally adopted.But the technology that is adopted in the world at present all is sectional, trans-regional, the operation of being interrupted, so have certain defective aspect processing efficiency, energy-conservation, automatization and the simplification.Japan has proposed brand-new " molten iron is handled continuously " notion recently, by the desiliconization of hot metal of trans-regional interruption, dephosphorization, desulfurization treatment process intensification, serialization, thereby reaches the purpose of minimum investment, the energy and the resources effective utilization of equipment.
Though anti-material of existing hot metal pretreatment or the anti-material of molten iron trough have use properties preferably, they all be sectional type, use the construction or repair of can often stopping by phased manner.And the molten iron continuous processing technique is a continuous uninterrupted, also must be long-life so require its anti-material, avoid repairing, so the chute refractory materials must have the quality of better use properties and Geng Gao than existing anti-material as far as possible.When carrying out the continuous pretreatment technology of molten iron in addition, to carry out desiliconization, desulfurization, the dephosphorization treatment of molten iron continuously, impossible total overall reaction is complete in reactor, so in chute, just continue to take place these three chemical reactions that take off, three slags that take off agent and reaction can produce the intensive erosion action to the chute refractory materials, cause the damage of refractory materials, also will bear washing away and mechanical wear of high temperature liquid iron.Therefore the refractory materials of molten iron continuous processing technique requirement must have better anti-melting slag, iron erosion performance and hot strength.
Patent CN1250041A " refractory material for molten iron tank of iron mixing furnace ", it is formed the employing superfine and heavily burns alumina aggregate, SiO
2Micro mist, cement, brown alundum powder, Al
2O
3Micro mist, molten iron tank reclaiming material, steel fiber.This patent is introduced its slag corrosion resistance, scour resistance is good, long service life, but the refractory materials that should invent can only obviously can not satisfy the needs of " molten iron is handled continuously " technology with 15 days.
Patent CN1030095A " Refractory Castables for BF Troughs and Runners " is that the most typical and widespread use both at home and abroad casting house (groove) is used refractory materials, it is main raw material that this material adopts brown corundum, suitably allocate silicon carbide, carbonaceous material, clay, high-alumina cement into, super-fine powder, admixture and make.Wherein brown corundum 60～80, SiC10～30, clay 1～5, high-alumina cement 2～5, super-fine powder 1～5, admixture 0.3～1.0.This patented material is mainly used on the blast furnace iron outlet groove, in use will just can reach higher life cycle through repairing repeatedly.This patented material is used for blast furnace tapping main channel, common hot metal pretreatment of in tap drain, not taking off Si, S, P, so working conditions is fine.
Japanese Patent JP570248 " Monolithic refractory for blast-fumace molteniron runner " has introduced the anti-material of a kind of blast furnace iron outlet groove, it is made up of aluminum oxide, silicon carbide, carbonaceous material, the silica that also comprises 1～10wt% of particle diameter＜1mm, the steel fiber of 0.5～5wt%.The singularity of this material is to have added silica, makes material that bigger after-expansion be arranged, and improves its heat impact strength, reduces the crackle that produces in using, thereby improves the wearing quality of casting house.But this technologic material uses and is interrupted, so improve its thermal shock performance particularly important, has therefore added silica.But silica has been brought a large amount of SiO into
2, it is disadvantageous that this anti-slag to material, iron corrode, thereby can influence work-ing life; It also is in order to improve thermal shock resistance that steel fiber adds, but when molten iron was more than 1400 ℃, steel fiber was easy to deterioration by oxidation, influenced material property on the contrary.The continuous pre-treatment of molten iron is to use continuously to refractory materials, and its variation of temperature is inviolent, and slag corrosion resistance and molten iron performance of flushing are the most important.So its technological approaches is worthless to the refractory materials of molten iron trough in the continuous pre-treatment of molten iron.
(3) summary of the invention
The object of the present invention is to provide a kind of non-oxide composite refractory materials for molten iron chute, this refractory materials is used for the continuous preprocessed molten iron chute of molten iron liner, has the longer life refractory materials of the performance of flushing of excellent slag corrosion resistance, antioxidant property, good volume stability and anti-slag, molten iron.
The present invention is achieved in that a kind of non-oxide composite refractory materials for molten iron chute, it is characterized in that forming (wt%) and comprise corundum material 50～70%, silicon carbide 15～30%, silicon nitride 3～10%, alumina powder 3～10%, carbon material 1～5%, oxidation inhibitor Si1～3%, the wedding agent silicon sol adds 6～15%, and a small amount of admixture comprises detonation suppressor and dispersion agent, adds 0.15～1.5% altogether.
Above-mentioned non-oxide composite refractory materials for molten iron chute, described silicon nitride are synthetic Si
3N
4Powder, its Chemical Composition Si
3N
4〉=85%; Silicon carbide is sic raw material, its SiC 〉=92%; The SiO of silicon sol
2Solids content 〉=25%; Corundum material is electric smelting compact alumina, white fused alumina, high alumina corundum, brown corundum and plate diamond spar one or more combination, adds its chemical ingredients Al with particle, fine powder or micro mist form
2O
3〉=90%; Carbonaceous material comprises graphite, pitch or electrode powder; Detonation suppressor is a metal A l powder, and add-on is 0.05～0.5%, and the dispersion agent add-on is 0.1～1.0%.
Erosion-resisting characteristics, the scour resistance of the present invention in order to improve the chute refractory materials adds part non-oxidized substance Si in the material
3N
4Raw material forms the non-oxidized substance composite refractory.The general applied raw material of refractory materials nearly all is an oxide compound, but the oxide refractories anti-erosion is not ideal enough.Along with the progress of refractory technology, increasing non-oxidized substance is applied in the refractory materials, and the elementary heat mechanical property of non-oxidized substance is anticorrosive, wear-resistant, but than being easier to oxidation.The silicon nitride fusing point is 1900 ℃, the intensity height, and thermal expansion is little, flexible.Because Si
3N
4With slag and iron all can not complete wetting, so its erosion-resisting characteristics is good; Its oxidation products can hinder the diffusion of oxidation in addition, plays the self-shield effect.Because in the chute refractory materials of silicon nitride comprising, use in being exposed to air, be oxidizing atmosphere, material sintering gradually in the use, its surface can form one deck tight zone, and it is further oxidized to hinder material.Also there are some researches show the Si of containing
3N
4Material is after high temperature uses, and the existence owing to nano level colloidal sol, activated alumina micro mist, SiC etc. in the matrix can generate a spot of Sialon phase, and the existence of this non-oxidized substance is highly beneficial to the erosion-resisting characteristics and the high-temperature behavior of material.Si in the material of the present invention
3N
4Be introduced as synthetic Si
3N
4Powder, add-on is 3～10%, requires its Chemical Composition Si
3N
4〉=85%.Si
3N
4Add-on is too many, and the improvement of material property is not obvious, and can cause the decline of normal temperature physicals, and the cost of material can be greatly improved simultaneously.
The another kind of non-oxidized substance that adopts in the material of the present invention is a sic raw material.Silicon carbide is to use the most effectively one of refractory raw material in the hot metal pretreatment system, and it is a kind of covalent linkage compound, has the characteristics of high-melting-point, high rigidity, high strength and low bulk, high-conductivity, extensive chemical stability.The coefficient of thermal expansion of SiC has only Al
2O
3Half.So add the aggressiveness that SiC can increase the antistripping of material and the slag of anti-the molten iron.Easily oxidation under oxidizing atmosphere, but also can form SiO
2Protective membrane and slow down or stop oxidation.Therefore also can protect the oxidation of carbon, the antistripping of carbon and erosion resistance are improved.Add-on is 15～30%, requires SiC 〉=92%.
Material of the present invention has adopted and the existing different coupling system of traditional unshape refractory, as wedding agent, and does not adopt mould material conventional junction mixture aluminous cement with silicon sol.One of technical progress of unshape refractory, the high cement amount → low cement content → ultra-low cement of former employing → developed into now non-cement mould material exactly.Because the calcium oxide of bringing in the cement can at high temperature react the production eutectic with the principal constituent in the refractory materials, thus the high-temperature behavior and the use properties of reduction refractory materials.So it is general few more good more as the cement consumption of wedding agent.Material of the present invention has been avoided the use of refractory cements, has adopted silicon sol as wedding agent.Silicon sol is the colloid that the silicon dioxide colloid particle evenly diffuses to form in water by the nanometer grade silica granulometric composition that is dispersed in the alkaline media.Alkaline media produces negative charge on silica dioxide granule, mutually exclusive, has produced stability.Because the positively charged ionic of other material of refractory materials exists or the variation of pH value (moisture evaporation), when repulsive interaction weakened, colloidal sol was transformed into gel.Hydroxyl in the process on the particle surface solidifies, and removes moisture, forms the Si-O-Si combination, produced deadlocked with combine, make refractory materials after construction, produce intensity.Pectisation is that condensation reaction disengages chemical attachment water institute extremely, is different from emitting of cement bonded chemically-bonded water, and is therefore highly beneficial to the draining baking of material.Adopt silicon sol as the wedding agent mould material following characteristics to be arranged: the middle hot strength height of (1) material, especially hot strength is higher more than 50% than traditional casting material strength, and middle adiabator intensity does not descend.And adopting cement as wedding agent, general medium temperature intensity is all on the low side.(2) material toasts drying easily, can not produce the baking crackle.Because when adopting silicon sol, do not need to add in addition water during the material construction, just the discharge of the free-water of pectisation as wedding agent.(3) the thermal shock resistance excellence of material.(4) sintering character of material is good, and intensity forms soon.(5) the viscosity ratio water of silicon sol is big, will get well the carbonaceous material avidity that adds when construction is stirred, and it is more even that material is stirred.The segregation of the floating or material of the carbonaceous material that produces when be difficult for producing the water cast.Add-on is 6～15%, can be according to mobile an amount of adding of construction material requested.It is some more to add the colloidal sol amount, and the self drainage of material can increase, but can cause the void content of material to increase, and volume density descends, and therefore decides according to construction requirement.The silicon sol that adopts requires SiO
2Solids content 〉=25%.
The main raw material that material of the present invention adopted is a corundum material.Can be electric smelting compact alumina, white fused alumina, high alumina corundum, brown corundum and plate diamond spar.Corundum itself has excellent chemical stability and antioxygenation, is a kind of senior refractory raw material.Main component Al in the corundum
2O
3Be a kind of to Na
2CO
3With iron scale extremely strong erosion-resistant oxide compound is arranged all, but simple Al
2O
3The coefficient of expansion is big, and spalling resistance is poor, and the matrix part is easily by the slag penetration melting loss.So simple Al
2O
3Material can not satisfy the needs of molten iron trough and hot metal pretreatment.Corundum can be one or more material combination addings wherein, and add-on 50～70% adds with particle, fine powder or micro mist form, requires its chemical ingredients Al
2O
3〉=90%.
Added carbonaceous material in the material of the present invention.Carbonaceous material comprises graphite, pitch or electrode powder.The carbonaceous material thermal expansion is low, has excellent permeability resistance and antistripping preferably, and the melts of metal and metal oxide is difficult to infiltration, is not subjected to the erosion of strong acid and strong base, with Al
2O
3, SiC, SiO
2Deng no congruent melting relation, be indispensable a kind of raw material therefore.Can add wherein one or both combinations, add-on is 1～5%.
Usually micro mist commonly used has SiO in the iron runner castable prior art
2Micro mist and Al
2O
3Micro mist.Add SiO
2Micro mist can improve normal temperature strength, acceleration of sintering, but the high-temperature behavior of goods and slag resistance are descended.Be wedding agent with the silicon sol in the material of the present invention, itself contain nano level SiO
2, under the medium and high temperature condition, be easy to material in Al
2O
3Generate mullite high temperature phase, make goods that better normal temperature strength and acceleration of sintering be arranged.So material of the present invention does not add SiO
2Micro mist, and only add Al
2O
3Micro mist, add-on 3～10%.
Material of the present invention also need add some special admixtures, comprises antioxidant, detonation suppressor, dispersion agent.Antioxidant mainly is a metal Si powder, and adding 1～3% is OK range.Detonation suppressor can be organic fibre or metal A l powder, and the technology of the present invention adopts the Al powder, and add-on is 0.05～0.5%.Metal A l powder not only helps the quick baking drying, and can its anti-oxidation effect.The dispersion agent add-on is controlled between 0.1～1.0% in the mould material.
Compare with present existing casting house or hot metal pretreatment chute, material of the present invention all has significant effect from the workability to the use properties.(1) adopted non-oxidized substance raw material silicon nitride and the silicon carbide that is particularly suitable for hot metal pretreatment technology, improved material greatly various molten iron have been handled the resistance to fouling that slag, three takes off agent, successive three is taken off treatment process better adaptability, further adapts to the long-life requirement of anti-material; (2) having adopted is the gel combination technology of wedding agent with the silicon sol.Because the characteristic of silicon sol, material have better flowability when construction, construction is short time of drying.In material of the present invention, nano level aerosil particles is high reactivity, easily with material in the mullite of the high resistivity against fire of aluminum oxide reaction generation, avoided eutectic that cement produces as wedding agent unfavorable result, so the refractoriness of material is higher, chemical stability is better to anti-material.In use silica gel can form protective layer around carbonaceous material, has stoped the oxidation of material.So material of the present invention has better oxidation-resistance, also improved the erosion-resisting characteristics of material simultaneously.
By the reasonable combination of each material, the erosion and the scouring capability of anti-molten iron of refractory materials of the present invention and slag are strong, have even, high dense structure, middle hot strength height, and heat-resisting shake good stability, material volume good stability, resistance of oxidation are strong.Therefore be particularly suitable for long-life target of the continuous pretreatment technology requirement of molten iron.
(4) embodiment
Table 1 is the main composition (wt%) of the embodiment of the invention and comparative example, and table 2 is the performance of inventive embodiments and comparative example sample.
Table 1
| Raw material | Embodiment | Comparative example | |||
| LX1 | LX2 | LX3 | ASCZ1 | ASCZ2 | |
| Compact alumina | 50 | 60 | 70 | 55 | 56 |
| Silicon carbide | 30 | 22 | 15 | 33 | 25 |
| Silicon nitride | 3 | 7 | 10 | 0 | 7 |
| Alumina powder | 9 | 6 | 3 | 4.0 | 3.5 |
| Carbon materials | 5 | 3 | 1 | 3 | 3 |
| Pure Silicon Metal | 3 | 2 | 1 | 2 | 2 |
| Aluminous cement | -- | -- | -- | 2 | 2 |
| Fine silica powder | -- | -- | -- | 1.0 | 1.5 |
| Detonation suppressor | +0.12 | +0.08 | +0.1 | +0.12 | +0.10 |
| Dispersion agent | +0.35 | +0.30 | +0.35 | +0.35 | +0.40 |
| Silicon sol | +12 | +10 | +6 | -- | -- |
| Amount of water | -- | -- | -- | +6.0 | +6.0 |
Table 2
| Project | LX1 | LX2 | LX3 | ASCZ1 | ASCZ2 | |
| Volume density g/cm 3 | 110℃×24h | 2.91 | 2.92 | 2.92 | 2.84 | 2.88 |
| 1000℃×3h | 2.87 | 2.89 | 2.89 | 2.80 | 2.81 | |
| 1450℃×3h | 2.88 | 2.90 | 2.91 | 2.81 | 2.83 | |
| Folding strength MPa | 110℃×24h | 6.3 | 6.5 | 6.9 | 4.1 | 5.3 |
| 1000℃×3h | 9.4 | 9.3 | 10.7 | 5.0 | 5.2 | |
| 1450℃×3h | 12.4 | 12.9 | 13.7 | 6.5 | 7.2 | |
| Compressive strength MPa | 110℃×24h | 20.7 | 21.3 | 23.0 | 19.1 | 20.3 |
| 1000℃×3h | 64.0 | 65.7 | 69.1 | 43.2 | 45.7 | |
| 1450℃×3h | 88.3 | 92.8 | 97.4 | 47.1 | 50.0 | |
| The anti-folding of high temperature, MPa | 1400℃×1h | 4.5 | 5.0 | 5.7 | 1.4 | 2.3 |
| Burn back line velocity of variation, % | 1450℃×3h | +0.39 | +0.4 | +0.37 | +2.01 *(1) | +1.78 *(1) |
| Oxidation-resistance *(2)Oxidated layer thickness, mm | After 1450 ℃ * 3h oxidizing atmosphere is burnt | The fine and close about 0.3mm oxidation bed thickness 5mm of glaze layer | The fine and close about 0.4mm oxidation bed thickness 5mm of glaze layer | The fine and close about 0.4mm oxidation bed thickness 5mm of glaze layer | Blister glaze layer 0.5～1mm, zone of oxidation 8mm | Blister glaze layer 0.5～1mm, zone of oxidation 6mm |
| Resistance to fouling *(3)Crucible corrodes mean thickness mm | Blast furnace granulated slag | 1.1 | 1.0 | 0.9 | 3.0 | 2.5 |
| Take off the Si slag | 3.1 | 3.0 | 3.0 | 4.0 | 3.5 | |
| Take off the P slag | 2.5 | 2.4 | 2.4 | 5.0 | 3.5 | |
Illustrate:
*(1) after sample carried out 1450 ℃ * 3h under oxidizing atmosphere, the adamantine layer of leachy blister, surface irregularity had appearred in ASCZ1, ASCZ2 surface.Error is arranged when measuring specimen size slightly, make data bigger than normal.
Annotate
*(2) antioxidant property is estimated by the sample oxidated layer thickness.Zone of oxidation is thick more, and oxidation-resistance is poor more.The embodiment sample burns back glaze laminar surface densification, intensity height; And comparative example sample glaze laminar surface is blister, and intensity is very low, drops easily.The antioxidant property that the embodiment sample is described is fine.
Annotate
*(3) crucible anti-erosion test.Specimen size 70 * 70 * 70mm, in the crucible hole of Φ 25 * 25mm is arranged.Be respectively charged into the blast furnace granulated slag fetched at the Baosteel scene, take off the Si slag, take off the P slag.Behind 1450 ℃ * 3h, cut crucible and observe the anti-erosion situation.All samples all leave more residue, illustrate that anti-slag permeates, the melting loss performance is good.The thickness that the embodiment sample is etched is all little than comparative example; And embodiment sample crucible shape is very complete, not distortion.Comparative example sample crucible corrodes the most serious, dented more obvious at slag, sidewall of crucible, air interface place.The erosion-resisting characteristics to various slags that shows the embodiment sample is all very excellent.
Analyze from technical indicator, comparative example is owing to adopted cement and silicon powder, and medium temperature intensity and high temperature hot strength also finally can have influence on the use properties of material all than inventive embodiment difference.
Material of the present invention not only can be applicable on the molten iron trough of the continuous pretreating containers of molten iron, also be applicable to fully on the blast furnace tapping main channel of working conditions harshness, also can be used as hot metal ladle, metal mixer car, three takes off transportation molten iron such as spray gun and carries out the container of hot metal pretreatment, the refractory materials of equipment liner.
Claims (7)
1. non-oxide composite refractory materials for molten iron chute, it is characterized in that forming (wt%) and comprise corundum material 50～70%, silicon carbide 15～30%, silicon nitride 3～10%, alumina powder 3～10%, carbon material 1～5%, oxidation inhibitor Si 1～3%, the wedding agent silicon sol adds 6～15%, and a small amount of admixture comprises detonation suppressor and dispersion agent, adds 0.15～1.5% altogether.
2. non-oxide composite refractory materials for molten iron chute according to claim 1 is characterized in that silicon nitride is synthetic Si
3N
4Powder, its Chemical Composition Si
3N
4〉=85%.
3. non-oxide composite refractory materials for molten iron chute according to claim 1 is characterized in that silicon carbide is sic raw material, its SiC 〉=92%.
4. non-oxide composite refractory materials for molten iron chute according to claim 1 is characterized in that the SiO of silicon sol
2Solids content 〉=25%.
5. non-oxide composite refractory materials for molten iron chute according to claim 1, it is characterized in that corundum material is electric smelting compact alumina, white fused alumina, high alumina corundum, brown corundum and plate diamond spar one or more combination, add its chemical ingredients Al with particle, fine powder or micro mist form
2O
3〉=90%.
6. non-oxide composite refractory materials for molten iron chute according to claim 1 is characterized in that carbonaceous material comprises graphite, pitch or electrode powder, can add wherein one or both combinations.
7. non-oxide composite refractory materials for molten iron chute according to claim 1 is characterized in that detonation suppressor is a metal A l powder, and add-on is 0.05～0.5%, and the dispersion agent add-on is 0.1～1.0%.
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