CN102910917A - Magnesium-calcium-carbon refractory material - Google Patents
Magnesium-calcium-carbon refractory material Download PDFInfo
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Abstract
The invention relates to a magnesium-calcium-carbon refractor material, in particular to a refractory material for smelting, which belongs to the technical field of refractory materials for smelting. The magnesium-calcium-carbon refractor material contains 1-25 parts of carbon, 0.2-6 parts of a magnesium-zirconium alloy, 60-96 parts of a mixture of dolomite sand, magnesium-calcium sand and magnesium sand, and 2-5 parts of a carbon-containing bonding agent, wherein the magnesium-zirconium alloy contains 3-35 percent of a zirconium element and the balance of magnesium and a small quantity of impurities. The magnesium-calcium-carbon refractor material provided by the invention can be taken as a refractory material for smelting, and has the advantages of oxidation resistance, high temperature resistance, slag permeation resistance, thermal shock resistance and easiness in producing.
Description
Technical field
The present invention relates to a kind of magnesium-calcium-carbon refractory materials, specifically a kind of metallurgy is used refractory materials, belongs to the metallurgy technical field of refractory materials.
Background technology
The magnesium lime refractory is a kind of basic refractory, just is used as the furnace lining material of steel-making converter from the beginning of the sixties in last century, for China's converter steelmaking industrial expansion has been made contribution.To the end of the eighties in last century, because applying of magnesia carbon brick sharply reduces the consumption of magnesium lime refractory, almost be eliminated, only have only a few producer to use.Entered since this century, fast development along with China's stainless steel and Clean Steel production, various magnesium lime refractories come into one's own again with its distinctive use properties, lower price with in the advantage aspect the environmental protection, be applied in large quantities on the refining unit of the senior steel grades such as stainless steel and Clean Steel at present, and with faster speed development.Its manufacturer is on the increase, and range of product and output constantly increase, and quality product improves constantly, and Application Areas constantly enlarges.
At present, the calcareous goods of typing magnesium of China mainly comprise magnesia-calcium brick and unfired magnesia-calcium carbon brick etc.So magnesia-calcium-carbon brick is better than the magnesia-calcium brick that high temperature burns till owing to contain the stability that carbon element uses, and it does not need high-temperature firing, and the magnesia-calcium brick that production energy consumption and cost are also fired far below needs is so the magnesia-calcium-carbon brick proportion strengthens gradually.
Magnesia-calcium-carbon brick is the refractory product of making take dolomite sand, calcium magnesia sand, magnesia and carbon element as main raw material.Its main advantage is that resistance to fouling, the heat-shock resistance under low basicity, suboxide iron iron blast furnace slag and the vacuum condition is better than magnesia carbon brick, also helps the oxygen level that reduces molten steel and is mingled with.The major subjects of magnesia-calcium-carbon brick is to improve hydration resistance, suitable antioxidant, the raising heat-shock resistance of selection.
The antioxidant that carbon containing refractory is commonly used has aluminium powder, silica flour, norbide etc.Need to add the antioxidant of elements such as containing Al, Si, B for the oxidation-resistance that improves magnesia-calcium-carbon brick.According to phasor, add the melting point depression that the elements such as Al, Si, B can make the refractory materials material in the magnesium calcareous material.
MAGNESIUM METAL, calcium metal are the desirable antioxidants of magnesia-calcium-carbon brick in theory.The MAGNESIUM METAL of the interpolation in the magnesia-calcium-carbon brick magnesium steam that rear evaporation produces that is heated forms dystectic MgO tight zone in the oxidation of magnesia-calcium-carbon brick hot side.This tight zone can stop the oxidation of carbon element, makes again product surface fine and close, improves hydration resistance and resistance to fouling.The oxidation products of magnesium is magnesium oxide, can not make the melting point depression of magnesium lime refractory.But the MAGNESIUM METAL activity is very high, no matter be all reactions such as easy and oxygen, carbonic acid gas, water when normal temperature is preserved or in the production process at magnesia-calcium-carbon brick.Just no longer possesses the effect of antioxidant after the MAGNESIUM METAL reaction.The high reactivity of MAGNESIUM METAL, inflammable and explosive property also make it be difficult to become the antioxidant of magnesia carbon brick.The activity of calcium metal is higher, more is difficult to be employed.
Summary of the invention
The object of the present invention is to provide a kind of mg-ca-carbon refractory, its oxidation-resistance, heat-shock resistance and shock resistance are improved synchronously.
Technical scheme of the present invention: formula rate is as follows by weight: magnesium oxide, 64 ~ 96 parts of calcium oxide raw materials, 1 ~ 25 part of carbon element, 0.2 ~ 6 part of Mg-Zr alloys, 2 ~ 5 parts of used for refractory material carbon-containing bonding agents.Described Mg-Zr alloys is powdery, and its granularity is less than or equal to 0.25mm; Zirconium content is 3% ~ 35% in the Mg-Zr alloys, and all the other are magnesium and impurity.
Described magnesium oxide, calcium oxide raw material are one or both in calcium magnesia sand or the dolomite sand, perhaps the mixture of one or both and magnesia; Described magnesium oxide, calcium oxide raw material are divided into particle and fine powder.Calcium magnesia sand, dolomite sand and magnesia all are dystectic refractory materialss, are main component and the skeletons of product of the present invention.CaO content in the invention product 〉=2.5%.
Carbon element is one or more in graphite, carbon black and the needle coke.Carbon element has very high fusing point.Carbon structure all is not easy to be infiltrated by molten metal, slag, can stop molten metal under the high temperature, slag to permeate to the invention interiors of products.Carbon element also has the low characteristics of coefficient of thermal expansion.The coefficient of thermal expansion of invention product reduces because of the existence of carbon element, so invention product volume stability in applied at elevated temperature is good, built-in thermal stress is low, and heat-shock resistance is strong.
MAGNESIUM METAL all is considered to have the refratory material antioxidant agent of advantage for a long time.The MAGNESIUM METAL fusing point is 648.9 ℃, and boiling point is 1090 ℃, and burning-point is 300 ~ 650 ℃, because its high reactivity is difficult to use in product of the present invention.The fusing point of zirconium is 1852 ± 2 ℃, and boiling point is 4377 ℃, has excellent corrosion resistance.Zirconium can Refining Mg Alloy crystal grain, improve the erosion resistance of magnesium; Zirconium also is the main adding elements in the antiflaming magnesium alloy.The reactive behavior of Mg-Zr alloys is well below MAGNESIUM METAL, can reduce metal in the manufacturing processed of invention product and H
2O, O
2Deng the consumption that brings of reaction.The low activity of Mg-Zr alloys also makes in the manufacturing processed of invention product and is not easy to occur deflagration accident having, and security is higher.
Mg-Zr alloys has precedence over carbon element in the invention product and the effect that stops the carbon element oxidation is played in the oxidizing substance reaction.The Mg-Zr alloys of invention interiors of products is heated rear magnesium steam raising to the hot side of invention product, and the Mg-Zr alloys of hot side together and O
2, CO
2, the reaction of the oxidizing substances such as CO, FeO, generate the magnesium oxide tight zone.The generation of magnesium oxide tight zone is conducive to improve the invention product in the density of hot side, can improve resistance to fouling and permeability resistance to slag, can further improve the oxidation-resistance of product, can also improve the anti-hydratability of invention product.
The oxidized rear generation ZrO of Zr in the Mg-Zr alloys
2Zirconium white is a kind of high grade refractory.Zirconium white occurs with monoclinic phase at normal temperatures, becomes Tetragonal to 1100 ℃ of left/right rotations in the temperature-rise period, and this phase transformation is reversible.Zirconium white can produce larger volumetric shrinkage at monoclinic phase in tetragonal phase converting, can be converted into again monoclinic phase in the time of cooling and follow larger volumetric expansion.The reversible transformation that zirconium white has causes it to shrink with the temperature raising in certain temperature range internal volume, reduces with temperature and expands.This and the opposite behavior of thermal expansion other material causes easily and contain heating up or cracking during cooling of zirconic goods about 1000 ℃.Zirconium white is followed volume and change of shape when being changed to monoclinic phase by Tetragonal (martensitic transformation), the energy absorbed energy, slow down the stress concentration of crack tip, Anticrack, thus toughness of material improved, comprise that stress-induced phase transformation is toughness reinforcing, crackle is crooked toughness reinforcing and tiny crack is toughness reinforcing.Zirconic phase transformation also helps the reduction of the coefficient of thermal expansion of refractory product integral body.Because ZrO
2The heat-shock resistance that has the invention product, the ability that anti-fracture is peeled off improve greatly.
The oxidation products of Mg-Zr alloys is dystectic magnesium oxide and zirconium white, can obviously not reduce the heat-resisting ability of invention product.
Described binding agent for carbonic refractory material is one or more in pitch liquation, tar liquid, liquid phenolic resin or the anhydrous binder for refractory material.Wherein novolac resin liquid wedding agent need add the part urotropine as solidifying agent.
The preparation method of described magnesium-calcium-carbon refractory materials is divided into two kinds of cold-forming and thermoformings, and step is as follows:
Cold-forming:
(1) preparation of pre-mixing fine powder: magnesium oxide, calcium oxide raw material are divided into particle and fine powder, with magnesium oxide, calcium oxide raw material fine powder and the Mg-Zr alloys powder mixing in the mixing machine of packing into together, obtain the pre-mixing fine powder;
(2) preparation of pug: magnesium oxide, calcium oxide raw material particle are added in the mixing machine, add binding agent for carbonic refractory material, carbon element and step (1) gained pre-mixing fine powder and continue to mix, namely obtain pug after mixing;
(3) moulding: with the weighing of step (2) gained pug, add in the mould and use the pressing machine extrusion forming, obtain adobe; The kiln road is put in the gained adobe be heated to 120 ~ 330 ℃, baking 5 ~ 25h;
(4) packing: with waterproof packing after step (3) the gained adobe cooling, namely get the product mg-ca-carbon refractory.
Thermoforming:
(1) preparation of pre-mixing fine powder: magnesium oxide, calcium oxide raw material are divided into particle and fine powder, with magnesium oxide, calcium oxide raw material fine powder and the Mg-Zr alloys powder mixing in the mixing machine of packing into together, obtain the pre-mixing fine powder; In connection with the agent heating, be dewatered to moisture≤0.5%, insulation; Particulate material is heated.
(2) preparation of pug: heated magnesium oxide, calcium oxide raw material particle are added in the mixing machine, and the wedding agent, carbon element, the pre-mixing fine powder that add step (1) gained continue to mix, and namely obtain pug after mixing;
(3) moulding: with the weighing of step (2) gained pug, add in the mould and use the pressing machine extrusion forming, obtain adobe;
(4) baking: portioned product need to be put into the gained adobe kiln road and be heated to 300 ~ 450 ℃, insulation 3 ~ 20h;
(5) packing: with waterproof packing after step (3), (4) the gained adobe cooling, namely get the product mg-ca-carbon refractory.
Beneficial effect of the present invention: adopt the magnesium-calcium-carbon refractory materials of the technology of the present invention preparation, taken into account oxidation-resistance, high thermal resistance, anti-slag penetration, heat-shock resistance and produceability.
Embodiment
Content among the following embodiment is parts by weight.
Embodiment 1
Mg-ca-carbon refractory by weight proportioning is as follows: 10 parts in-198 graphite, 15 parts of needle cokes, 64 parts of dolomite sands, 6 parts in Mg-Zr alloys powder, 4.5 parts of the liquid phenolic resins of moisture＜0.5%, 0.5 part of urotropine.Wherein zirconium content is 10% in the Mg-Zr alloys powder, and granularity is less than 0.25mm.
The preparation method of described magnesium-calcium-carbon refractory materials, step is as follows:
(1) preparation of pre-mixing fine powder: the dolomite sand fine powder of granularity≤0.2mm and Mg-Zr alloys powder added in the mixing machine mix 20min, obtain the pre-mixing fine powder;
(2) preparation of pug: with mixing in dolomite sand particle and the urotropine adding mixing machine, add again liquid phenolic resin and mixed 5 minutes, add needle coke and graphite and continue to mix 15 minutes; Add again step (1) gained pre-mixing fine powder, mix obtaining pug after 10 minutes;
(3) moulding: with the weighing of step (2) gained pug, add in the mould and use the pressing machine extrusion forming, obtain adobe; With the adobe baking, top temperature is 200 ℃, toasts 10 hours;
(4) packing: with waterproof packing after step (3) the gained adobe cooling, namely get the product mg-ca-carbon refractory.
This product sample is pressed the oxidation-resistance that GB/T13244 detects 1000 ℃ * 3h, and the Decarburized layer mean thickness is 2.5mm.This product sample is pressed the heat-shock resistance that YB/T376.1 detects 1100 ℃-water-cooled.Sample stands 15 times test follower head and breaks.This product is used for stopper rod of tundish, and the life-span can reach 25 hours.
Embodiment 2
Mg-ca-carbon refractory by weight proportioning is as follows: 2 parts in-194 graphite, and 1 part of N220 carbon black, 80 parts of dolomite sands, 12 parts in magnesia, 3 parts in Mg-Zr alloys powder, 2 parts in coal tar, wherein zirconium content is 3% in the Mg-Zr alloys powder, granularity is less than 0.25mm.
The preparation method of described magnesium-calcium-carbon refractory materials, step is as follows:
(1) preparation of pre-mixing fine powder: granularity packed into together less than the magnesia powder of 0.074mm and Mg-Zr alloys mixed 10 minutes in the premixer, obtain the pre-mixing fine powder; To moisture＜0.3%, and insulation makes it keep liquid the coal tar thermal dehydration.
(2) preparation of pug: mix adding in the mixing machine after the heating of dolomite sand particle, then the tar that adds heat mixed 2 minutes, adding-194 graphite mixed 2 minutes, added carbon black and continued to mix 2 minutes, added the mixing of step (1) gained pre-mixing fine powder again and obtained pug in 10 minutes.
(3) moulding: with the while hot weighing of step (2) gained pug, add in the mould and use the pressing machine extrusion forming, obtain adobe.
(4) packing: with waterproof packing after step (3) the gained adobe cooling, namely get the product mg-ca-carbon refractory.
This product sample is pressed the oxidation-resistance that GB/T13244 detects 1000 ℃ * 3h, and the Decarburized layer mean thickness is 2.5mm.This product sample is pressed the heat-shock resistance that YB/T376.1 detects 1100 ℃-water-cooled.Sample can stand 7 times test and crackle not occur.This product is applicable to make steel refining furnace, electric furnace, converter slag lining.
Embodiment 3
Mg-ca-carbon refractory by weight proportioning is as follows: 1 part of N220 carbon black, and 50 parts of dolomite sands, 46 parts of calcium magnesia sands, 0.2 part in Mg-Zr alloys powder, 2.8 parts of mid-temperature pitches, wherein the ratio of zirconium is 35% in the Mg-Zr alloys, granularity is≤10 microns.
(1) preparation of pre-mixing fine powder: the fine powder of granularity≤0.1mm in calcium magnesia sand, the dolomite sand and Mg-Zr alloys powder are added in the premixer, be pre-mixed evenly, obtain the pre-mixing fine powder;
(2) preparation of pug: to 160 ℃, insulation is to emerge moisture content＜0.2% without steam with mid-temperature pitch heating liquefaction; Be that the dolomite sand of 6-0.1mm and calcium magnesia sand particle are heated to 200 ℃ and send in the mixing machine and mix with granularity, pour pitch liquation mixings 2min into after mixing 1min, add the N220 carbon black and stir 2min, add again step (1) gained pre-mixing fine powder mixing 15 minutes; After mixing end pug is put into insulated tank;
(3) moulding: with the weighing of step (2) gained pug, extrusion forming in 1000 tons of friction press stock moulds of rear adding obtains adobe; The kiln road is put in the adobe of gained be heated to 320 ℃ ± 10 ℃, be incubated 5 hours, kiln discharge;
(4) packing: with waterproof packing after step (3) the gained adobe cooling, namely get the product mg-ca-carbon refractory.
This product sample is pressed the oxidation-resistance that GB/T13244 detects 1000 ℃ * 3h, and the Decarburized layer mean thickness is 4mm.This product sample is pressed the heat-shock resistance that YB/T376.1 detects 1100 ℃-water-cooled.Sample can stand 5 times test and crackle not occur.This product is used for RH stove lower channel place, can substitute poisonous magnesia chrome brick.
Claims (6)
1. a mg-ca-carbon refractory is characterized in that institute's mg-ca-carbon refractory formula rate is as follows by weight: magnesium oxide, 64 ~ 96 parts of calcium oxide raw materials, 1 ~ 25 part of carbon element, 0.2 ~ 6 part of Mg-Zr alloys, 2 ~ 5 parts of binding agent for carbonic refractory material.
2. described mg-ca-carbon refractory according to claim 1, it is characterized in that: the granularity of described Mg-Zr alloys is less than or equal to 0.25mm; Zirconium content is 3% ~ 35% in the Mg-Zr alloys, and all the other are magnesium and impurity; Mg-Zr alloys is powdery.
3. described mg-ca-carbon refractory according to claim 1, it is characterized in that: described carbon element is one or more in graphite, carbon black and the needle coke.
4. described mg-ca-carbon refractory according to claim 1, it is characterized in that: described magnesium oxide, calcium oxide raw material are one or both in calcium magnesia sand or the dolomite sand, perhaps the mixture of one or both and magnesia; Described magnesium oxide, calcium oxide raw material are divided into particle and fine powder.
5. mg-ca-carbon refractory according to claim 1, it is characterized in that: described binding agent for carbonic refractory material is the mixture of pitch liquation, tar liquid, novolac resin liquid and urotropine, or in the anhydrous binder for refractory material one or more.
6. described magnesium-calcium-carbon refractory materials according to claim 4 is characterized in that: the content of CaO 〉=2.5% in the described mg-ca-carbon refractory.
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| CN107176844A (en) * | 2017-05-11 | 2017-09-19 | 长兴县煤山工业炉料有限公司 | A kind of magnesium-calcium-carbon refractory material |
| CN107935611A (en) * | 2018-01-03 | 2018-04-20 | 武汉科技大学 | A kind of calcium zirconium carbon refractory and preparation method thereof |
| CN108178642A (en) * | 2018-01-24 | 2018-06-19 | 合肥铭佑高温技术有限公司 | A kind of hydration-resisting alkalinity high-temperature refractory and preparation method thereof |
| CN109133945A (en) * | 2018-08-09 | 2019-01-04 | 宁国市挚友合金钢材料有限公司 | A kind of furnace inner lining weather-proof insulating materials and preparation method thereof |
| CN109133890A (en) * | 2018-09-28 | 2019-01-04 | 佛山齐安建筑科技有限公司 | A kind of preparation method of anticorrosive pressure-resisting type bearing bricks |
| CN112341161A (en) * | 2020-10-26 | 2021-02-09 | 北京利尔高温材料股份有限公司 | Anti-stripping unburned magnesium-calcium-carbon brick and preparation method thereof |
| CN112341161B (en) * | 2020-10-26 | 2022-06-24 | 北京利尔高温材料股份有限公司 | Anti-stripping unburned magnesium-calcium-carbon brick and preparation method thereof |
| CN112390654A (en) * | 2020-11-30 | 2021-02-23 | 邯郸市翰润达耐火材料有限公司 | Refractory material and preparation method and application thereof |
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