CN102180685B - Air-permeable brick for converter - Google Patents
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- CN102180685B CN102180685B CN 201110057369 CN201110057369A CN102180685B CN 102180685 B CN102180685 B CN 102180685B CN 201110057369 CN201110057369 CN 201110057369 CN 201110057369 A CN201110057369 A CN 201110057369A CN 102180685 B CN102180685 B CN 102180685B
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Abstract
The invention provides an air-permeable brick for a converter. The air-permeable brick at least consists of the following raw materials in part by weight: 30 to 50 parts of electrofused magnesia particles with the particle size of 1 to 3mm, 20 to 40 parts of electrofused magnesia particles with the particle size of 0 to 1mm, 20 to 40 parts of electrofused magnesia powder with the particle size of 0 to 0.088mm, 5 to 25 parts of electrofused spinel fine powder with the particle size of 0 to 0.044mm, 10 to 30 parts of flake graphite, 5 to 8 percent of liquid bonding agent and 3 to 8 parts of composite antioxidant with the particle size of 0 to 0.088mm, wherein the composite antioxidant consists of molybdenum disilicide and metal powder in a weight part ratio of 1:9-1:1. The air-permeable brick has high erosion resistance and oxidation resistance.
Description
Technical field
The present invention relates to a kind of gas permeable brick, be specially a kind of gas permeable brick for converter.
Background technology
Gas permeable brick is a kind of important refined steel ladles fire resistive material product, in Practical Project uses, gas permeable brick faces following problem all the time: the first, Spalling resistance can be poor, gas permeable brick in use contacts the molten steel of high temperature, make gas permeable brick produce very large thermal stresses, can make like this gas permeable brick vary in size due to the effect of surface local thermal stresses of its contact molten steel and the effect of central hot stress, after life-time service, cause the surface layer peeling of gas permeable brick contact molten steel.The second, erosion-resisting characteristics is poor, and the Corrosion rate that shows as significantly gas permeable brick in use procedure at present is large, and the height of the rear residual brick that deteriorates can't reach engineering demand.Three, permeability is unstable, owing to there being a large amount of impurity in molten steel, can fall the ventilation property that easily affects gas channel in gas permeable brick on gas permeable brick after Impurity deposition.
Also just because of above-mentioned three problems, so the refining ladle domestic demand will be changed gas permeable brick aperiodically, and also need again to bake bag after changing, so just affected the normal operation of refining ladle, reduced working efficiency.And the gas permeable brick in converter in use can not be changed, and due to the long service life of converter, up to up to ten thousand times.Therefore the use properties of converter air brick is had relatively high expectations.In above-mentioned three problems, the first two problem can realize by the raw material of reasonable, so at fire resisting material field, seek the emphasis that Spalling resistance energy and the good gas permeable brick of erosion-resisting characteristics have become technical study.
in prior art, Chinese patent CN101492297A discloses a kind of bottom blowing orienting stephanoporate air brick body for electric furnace, this air brick body is made by weight ratio by following raw material: 1 part of the electrosmelted magnesite clinker of≤5.0mm, 0.8 ~ 1 part of the electrosmelted magnesite clinker of≤3.0mm, 0.8 ~ 1 part of the electrosmelted magnesite clinker of≤1.0mm, 200 0.3 ~ 0.5 part of purpose electrosmelted magnesite clinker fine powder, 0.8 part of high purity graphite, 0.1 ~ 0.2 part of additive, 0.15 part of wedding agent, wherein wedding agent is resol, additive is by weight percentage by 40 ~ 60% aluminium powders, 20 ~ 40% aluminium-magnesium alloy powders, 5 ~ 15% carborundum powders are made.All be added with graphite in the gas permeable brick of prior art, the major cause of adding graphite is its performance with good difficult infiltration, can increase like this erosion-resisting characteristics of refractory materials.Although, in this technology, added aluminium powder as additive, because the chemical activity of aluminium is good, it has better oxidation competitive edge for graphite, so effect that the existence meeting of aluminium powder is certain to the anti-oxidant generation of graphite, but from its addition, only only less than 0.15 part, on essence, the interpolation of the additive of above-mentioned weight part can effectively not act on the anti-oxidant generation of graphite, in case and graphite has produced oxidation, it be difficult for to infiltrate and the characteristics that can increase the refractory materials erosion-resisting characteristics will not exist so.Will the performance of air brick body be impacted.
In fire resisting material field, the stability that improves graphite by adding metal powder is the technique means of habitually practising the most.Certainly, as those skilled in the art, it can expect realizing protection to graphite stability by the addition that improves additive.But, for above-mentioned technology, even if add metal powder as much as possible; also just from the chemical stability of graphite, it is protected merely; namely pass through to guarantee the chemical stability of graphite, thereby can utilize graphite to be difficult for the characteristic that infiltrates, prevent that molten steel from corroding gas permeable brick.But, in above-mentioned technology, the umber of graphite and little during the raw material of gas permeable brick forms, the resistance to fouling that so simple dependence graphite improves gas permeable brick is not to be effective means, should consider that the characteristic that further is difficult for infiltrating by graphite on the basis of building gas permeable brick raw material formation dense structure improves the resistance to fouling of gas permeable brick, can't form any effect of dense structure generation to the gas permeable brick raw material and add metal powder in above-mentioned technology, so the resistance to fouling of the gas permeable brick for preparing is still very poor.
Wolfram varbide is the black hexagonal, and hardness and diamond are close, and its fusing point reaches 2870 ℃, and boiling point is electric, hot good conductor up to 6000 ℃.The chemical property of wolfram varbide is very stable.
Molybdenum disilicide is the highest a kind of middle phase of silicon content during molybdenum-silicon binary alloy is, it is compound between the fixing dalton's shaped metal of composition, having the dual nature of metal and pottery, be a kind of high-temperature material of excellent performance, and it has lower thermal expansivity.
Summary of the invention
Technical problem to be solved by this invention is that gas permeable brick of the prior art guarantees the chemical stability of graphite by adding metal powder, but the interpolation of metal powder does not form dense structure generation effect to the gas permeable brick raw material, cause the gas permeable brick resistance to fouling poor, and then a kind of composite antioxidant that can guarantee the graphite chemical stability, help to form simultaneously the gas permeable brick dense structure, gas permeable brick with good resistance to fouling of being added with is provided.
In order to solve the problems of the technologies described above, the invention provides a kind of gas permeable brick, the raw material by following weight part forms at least:
Electrosmelted magnesite clinker particle: 30～50 parts of grain diameter 3～1mm
Electrosmelted magnesite clinker particle: 20～40 parts of grain diameter 1～0mm
Electrofusion magnesia powder: 20～40 parts of particle diameter 0.088～0mm
Electric smelting spinel fine powder: 5～25 parts of particle diameter 0.044～0mm
Crystalline flake graphite: 10～30 parts
Liquid wedding agent: 5～8 parts
Composite antioxidant: 3～8 parts of particle diameter 0.088～0mm
Described composite antioxidant is comprised of molybdenum disilicide and metal powder, and the portion rate of described molybdenum disilicide and described metal powder is 1:9 ~ 1:1.
The portion rate of described molybdenum disilicide and described metal powder is 1:7.
Described metal powder is the mixture of magnesium powder, aluminium powder and silica flour.
The portion rate of described molybdenum disilicide and described magnesium powder, aluminium powder, silica flour is 1:4:1:2.
Described liquid wedding agent is the mixture of at least a or resol and polyalcohols at least a or polyalcohols in resol; In described polyalcohols, the quantity of hydroxyl is more than or equal to 3.
Described gas permeable brick also comprises the wolfram varbide of 3 ~ 6 weight parts, and the particle diameter of described wolfram varbide is less than 100nm.
Described gas permeable brick comprises the component of following weight percent: Al at least
2O
3: 5～16%, MgO:60～80%, C:10～22%.
Gas permeable brick of the present invention has following advantage:
(1) gas permeable brick of the present invention, the electrosmelted magnesite clinker that selection hardness is large, heat is shaken good stability, load softening point is high, chemical resistance of concrete is good and electric smelting spinel are as the aggregate of gas permeable brick, and limit described grain diameter, size distribution rationally is set, avoid causing greatly the gas permeable brick pore after moulding many because of grain diameter, between aggregate, the gap is large, and molten steel is via aggregate gap infiltration; Gas permeable brick of the present invention has also added the electrofusion magnesia powder of certain part by weight, thereby utilize the matching coordinative mechanism of action between particle and powder, after the one-piece construction framework of electrosmelted magnesite clinker and electric smelting spinel particle formation Gunning refractory, it is inner that powder can enter this framework, carrying out the further filling of framework supports, and in the adhesion property that has strengthened under the effect of wedding agent between particle and powder, simultaneously also make the compactness of gas permeable brick greatly improve, further reduced the possibility that molten steel enters via the aggregate gap; Crystalline flake graphite is wrapped in particle surface or is scattered in powder, and utilizes it to be difficult for the characteristic that is infiltrated by molten steel, prevents that molten steel from entering gas permeable brick inside.
of paramount importancely be, select composite antioxidant as the stablizer of crystalline flake graphite in gas permeable brick of the present invention, and composite antioxidant must be comprised of molybdenum disilicide and metal powder, the results showed, the composite antioxidant of above-mentioned composition, by limiting the suitable weight part ratio of described composite antioxidant, and in described composite antioxidant the portion rate of molybdenum disilicide and metal powder, adopt metal powder to promote the formation of magnalium-spinel dense structure as the water-permeable brick of antioxidant compared to prior art, the formation of magnalium-spinel dense structure makes the aggregate gap after electrofusion magnesia powder is filled significantly reduce, significantly improved the resistance to fouling of gas permeable brick.
(2) gas permeable brick of the present invention, further added wolfram varbide as feed composition, and the particle diameter that limits described wolfram varbide is nanometer particle size, the tungsten carbide particle that particle diameter is less has good dispersiveness, on the one hand, can wrap up well and protect graphite particle after wolfram varbide adds, make graphite to keep stable existence under the medium and high temperature condition, avoid wetting and be damaged by molten steel; On the other hand, the interpolation of nanometer tungsten carbide is a part of aggregate of filling gap further, has reduced the oxidized possibility of graphite, has improved resistance to fouling and the oxidation-resistance of gas permeable brick.
(3) gas permeable brick of the present invention uses the polyalcohols organism as wedding agent, and such wedding agent is combined with graphite than liquid resin is easier, can form better the protective layer to graphite, has strengthened the anti-molten steel aggressiveness of graphite.
Description of drawings
Fig. 1 is the structural representation of static anti-slag crucible.
Embodiment
For content of the present invention is more likely to be clearly understood, the below is described in further detail according to a particular embodiment of the invention
The raw material of gas permeable brick forms
Limiting the electrosmelted magnesite clinker grain diameter in above-described embodiment is 1～0mm, 0.088 ~ 0mm does not conflict with described electrofusion magnesia powder grain diameter, this is the phraseology that those skilled in the art commonly use, described electrosmelted magnesite clinker grain diameter is 1～0mm, represent described electrosmelted magnesite clinker grain diameter less than 1mm, and still belong in the particle size range of particle.
Gas permeable brick of the present invention, the quantity that limits hydroxyl in described polyalcohols is more than or equal to 3, illustrates that namely polyvalent alcohol can be to comprise that the hydroxyl quantity of trivalent alcohol is at the alcohols more than 3.
The crystalline flake graphite that uses in gas permeable brick of the present invention can be commercially available any crystalline flake graphite.
gas permeable brick of the present invention in the preparation, the first step, the preparation pug, first the electrosmelted magnesite clinker particle of the variable grain particle diameter of specified weight part is added in mixing pan and mix, the liquid wedding agent that adds specified weight part in the mixed electrosmelted magnesite clinker particle, above-mentioned substance is stirred, after stirring, add wherein again the crystalline flake graphite of specified weight part and stir, the last electrofusion magnesia powder of specified weight part that adds wherein again, the mixture of electric smelting spinel fine powder and composite antioxidant, perhaps electrofusion magnesia powder, electric smelting spinel fine powder, the mixture of composite antioxidant and wolfram varbide, obtain pug after mixed grind is even.
Second step, compression moulding adopts isostatic pressing machine of the prior art to suppress, and perhaps uses friction press to suppress.
When using the isostatic pressing machine compacting, operating method is divided into two kinds, and a kind of is first pressed brick core, and is then coarse the processing of the brick wicking surface after the demoulding, reinstalls mould, adds pug on every side, secondary compression moulding.The second is directly pug to be added in mould, a compression moulding.In any case, all to first fix the metal thin tube of air feed, and carry out sfgd., slowly reinforced, prevent that metal thin tube from stopping up or tilting.
When using the friction press compacting, can disposal pressed moulding, the static pressure repressed brick core such as also can use, fill it up with material around the brick core after, the compacting of use brick pressing machine, certainly sometimes for efficient and convenient, ramming process after the brick core adds pug on every side, also a kind of molding mode, be the aspects such as the gas permeable brick produced of this mode is close at body, intensity, work-ing life all than etc. the static pressure compacting or brick pressing machine compacting poor.
The 3rd step, sharp processing, the gas permeable brick of generally producing, guaranteeing in its highly satisfactory situation, other sizes are all bigger than normal a little, need to become qualified size with machined into, finally be the truncated rectangular pyramids shape that meets the drawing requirement rule, namely obtain gas permeable brick after then toasting, spray antioxidizing paint, rebake.
Test case
For oxidation-resistance and the resistance to fouling of gas permeable brick that the above embodiment of the present invention is prepared characterizes, adopted following experiment to carry out:
Test name: anti-slag test
Oxidation-resistance testing method: compacting sample, preparation method by the gas permeable brick described in above-described embodiment prepares pug, and be pressed into the square sample piece of 80 * 80 * 80mm, after the demoulding in a sidetracking hole, the diameter in hole is 35mm, dark is 35mm, makes static anti-slag crucible (see figure 1), then to static anti-slag crucible at 200 ℃ of lower drying treatment 24h.After dry the end, fill converter slag in the hole, be warmed up to from room temperature in oxidizing atmosphere that under 1600 ℃, insulation 3h burns till, then cooling, time remaining is longer, and oxidated layer thickness is thinner, and the antioxidant property of illustrative material is better.
Resistance to fouling testing method: compacting sample, preparation method by the gas permeable brick described in above-described embodiment prepares pug, and be pressed into the square sample piece of 80 * 80 * 80mm, after the demoulding in a sidetracking hole, the diameter in hole is 35mm, dark is 35mm, makes static anti-slag crucible (see figure 1), then to static anti-slag crucible at 200 ℃ of lower drying treatment 24h.After dry the end, fill converter slag in the hole, in non-oxidizing atmosphere and temperature be that under 1600 ℃, insulation 3h burns till, cooling rear vertical incision is observed slag to the erosion condition of material, corrodes layer thinner, perhaps the internal corrosion layer is not obvious, and the erosion-resisting characteristics of illustrative material is better.
Mensuration about testing data: because the antioxygen layer colour-change is apparent in view, so better measure, but because the existence in material endoparticle and space, so the thickness of zone of oxidation is not homogeneous, data are got the mean value of several projecting points, and the thickness of zone of oxidation is less than this numerical value.Corrode layer also same.
Can find out from above-mentioned data, gas permeable brick of the present invention is after adding the composite antioxidant that is comprised of molybdenum disilicide and metal powder, can be so that the oxide thickness of gas permeable brick and corrode layer thickness and greatly reduce, thus the performance of gas permeable brick improved to a great extent.
Obviously, above-described embodiment is only for example clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive, and the apparent variation of being extended out thus or the change still be among the protection domain of these real innovation and creation.
Claims (6)
1. a gas permeable brick, is characterized in that, the raw material by following weight part forms at least:
Electrosmelted magnesite clinker particle: 30～50 parts of grain diameter 3～1mm
Electrosmelted magnesite clinker particle: 20～40 parts of grain diameter 1～0mm
Electrofusion magnesia powder: 20～40 parts of particle diameter 0.088～0mm
Electric smelting spinel fine powder: 5～25 parts of particle diameter 0.044～0mm
Crystalline flake graphite: 10～30 parts
Liquid wedding agent: 5～8 parts
Composite antioxidant: 3～8 parts of particle diameter 0.088～0mm
Described composite antioxidant is comprised of molybdenum disilicide and metal powder, and the portion rate of described molybdenum disilicide and described metal powder is 1:9 ~ 1:1.
2. gas permeable brick according to claim 1, is characterized in that, the portion rate of described molybdenum disilicide and described metal powder is 1:7.
3. gas permeable brick according to claim 1 and 2, is characterized in that, described metal powder is the mixture of magnesium powder, aluminium powder and silica flour.
4. gas permeable brick according to claim 3, is characterized in that, the portion rate of described molybdenum disilicide and described magnesium powder, aluminium powder, silica flour is 1:4:1:2.
5. gas permeable brick according to claim 4, is characterized in that, described liquid wedding agent is the mixture of at least a or resol and polyvalent alcohol at least a or polyvalent alcohol in resol;
In described polyvalent alcohol, the quantity of hydroxyl is more than or equal to 3.
6. according to claim 1 and 2 or 4 or 5 described gas permeable bricks, is characterized in that, also comprises the wolfram varbide of 3 ~ 6 weight parts, and the particle diameter of described wolfram varbide is less than 100nm.
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| CN 201110057369 CN102180685B (en) | 2011-03-10 | 2011-03-10 | Air-permeable brick for converter |
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| CN 201110057369 CN102180685B (en) | 2011-03-10 | 2011-03-10 | Air-permeable brick for converter |
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| CN102180685A CN102180685A (en) | 2011-09-14 |
| CN102180685B true CN102180685B (en) | 2013-05-22 |
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| CN102775171B (en) * | 2012-08-15 | 2014-02-26 | 江苏苏嘉集团新材料有限公司 | Resin-bonded aluminum-magnesium refractory material |
| CN104016690B (en) * | 2014-05-30 | 2015-06-17 | 浙江自立股份有限公司 | A preparing method of a high-strength low-expansion magnesium spinel brick |
| CN104016691B (en) * | 2014-05-30 | 2016-06-08 | 浙江自立股份有限公司 | A kind of magnesia-spinel brick for RH vacuum refining furnace and preparation method thereof |
| CN105272306B (en) * | 2015-11-10 | 2019-02-01 | 首钢京唐钢铁联合有限责任公司 | Refractory brick and preparation method thereof |
| CN108546134A (en) * | 2018-03-28 | 2018-09-18 | 江苏苏嘉集团新材料有限公司 | A kind of no carbon brick and preparation method thereof |
| CN112110737B (en) * | 2020-09-23 | 2022-05-06 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | High-chromium refractory material and preparation method thereof |
| CN113045321A (en) * | 2021-01-14 | 2021-06-29 | 云南濮耐昆钢高温材料有限公司 | Low-carbon converter steel tapping hole casing brick |
| CN113800890A (en) * | 2021-08-06 | 2021-12-17 | 浙江红鹰集团股份有限公司 | Composition and forming method of high-oxygen slag scouring resistant composite magnesia carbon brick |
| CN115321996B (en) * | 2022-08-29 | 2023-09-22 | 中冶武汉冶金建筑研究院有限公司 | Iron runner castable containing submicron composite antioxidant and preparation method thereof |
| CN116178023A (en) * | 2023-02-21 | 2023-05-30 | 中钢集团洛阳耐火材料研究院有限公司 | Thermal shock resistant and oxidation resistant Si 3 N 4 Preparation method of combined SiC refractory material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1237562A (en) * | 1999-02-25 | 1999-12-08 | 宝山钢铁(集团)公司 | Anti-oxidizing agent for carbon-contained fireproof material |
| CN100551876C (en) * | 2007-12-21 | 2009-10-21 | 杨红 | Ultra-low-carbon steel slag inclusion line magnesium-carbon brick and production method thereof |
| CN101244940B (en) * | 2008-03-20 | 2013-11-06 | 郑州大学 | Metallic composite low carbon magnesium carbon brick for ladle slag wire and manufacture method thereof |
| CN101613207B (en) * | 2008-12-31 | 2012-08-29 | 北京利尔高温材料股份有限公司 | Low-carbon corundum spinelle brick for refined steel ladles and preparation method thereof |
| CN101492297A (en) * | 2009-02-27 | 2009-07-29 | 营口鲅鱼圈耐火材料有限公司 | Bottom blowing orienting stephanoporate air brick body for electric furnace and method of producing the same |
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Effective date of registration: 20171128 Address after: 457000 the Yellow River Road, Henan, Puyang Patentee after: PRCO Functional Refractories Co., Ltd. Address before: 457100 Puyang City, Henan Province West Ring Road in the middle Co-patentee before: Puyang Pu hi temperature material (Group) Limited by Share Ltd Beijing science and technology research and Development Center Patentee before: Puyang Refractories Group Co., Ltd. |
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