CN102910917B - 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 refractory materials, belongs to metallurgy technical field of refractory materials.
Background technology
Magnesium lime refractory is a kind of basic refractory, and the furnace lining material ，Wei China converter steelmaking industrial expansion that is just used as steel-making converter from the beginning of the sixties in last century has been made contribution.To the end of the eighties in last century, due to applying of magnesia carbon brick, the consumption of magnesium lime refractory is sharply reduced, be almost eliminated, only have only a few producer to use.Since entering this century, fast development along with China's stainless steel and Clean Steel production, various magnesium lime refractories are with its distinctive use properties, lower price and again come into one's own in the advantage aspect 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 speed development faster.Its manufacturer is on the increase, and range of product and output constantly increase, and quality product improves constantly, and Application Areas constantly expands.
At present, the calcareous goods of sizing magnesium of China mainly comprise magnesia-calcium brick and unfired magnesia-calcium carbon brick etc.So magnesia-calcium-carbon brick is better than owing to containing the stability that carbon element uses the magnesia-calcium brick that high temperature burns till, 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, so magnesia-calcium-carbon brick proportion strengthens gradually.
Magnesia-calcium-carbon brick is to take the refractory product that dolomite sand, calcium magnesia sand, magnesia and carbon element make 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 vacuum condition is better than magnesia carbon brick, also helps and reduces the oxygen level of molten steel and be mingled with.The major subjects of magnesia-calcium-carbon brick is raising hydration resistance, selects suitable antioxidant, improves heat-shock resistance.
The antioxidant that carbon containing refractory is conventional has aluminium powder, silica flour, norbide etc.In order to improve the oxidation-resistance of magnesia-calcium-carbon brick, need to add the antioxidant containing elements such as Al, Si, B.According to phasor, in magnesium calcareous material, add the melting point depression that the elements such as Al, Si, B can make refractory materials material.
MAGNESIUM METAL, calcium metal are the desirable antioxidants of magnesia-calcium-carbon brick in theory.The MAGNESIUM METAL of the interpolation in magnesia-calcium-carbon brick is evaporated the magnesium steam producing after being heated, and in the oxidation of magnesia-calcium-carbon brick hot side, forms dystectic MgO tight zone.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 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.After MAGNESIUM METAL reaction, just no longer possesses the effect of antioxidant.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, is more 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 synchronously improved.
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; In Mg-Zr alloys, zirconium content is 3% ~ 35%, and all the other are magnesium and impurity.
Described magnesium oxide, calcium oxide raw material are one or both in calcium magnesia sand or dolomite sand, or 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 are all dystectic refractory materialss, are main component and the skeletons of product of the present invention.CaO content >=2.5% in invention product.
Carbon element is one or more in graphite, carbon black and needle coke.Carbon element has very high fusing point.Carbon structure is all not easy to be infiltrated by molten metal, slag, can stop molten metal under high temperature, slag to permeate to invention interiors of products.Carbon element also has the feature that coefficient of thermal expansion is low.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 is all considered to have the refratory material antioxidant agent of advantage for a long time.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 is also the main adding elements in 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
2the consumption bringing Deng reaction.The low activity of Mg-Zr alloys also makes to be not easy to occur deflagration accident having in the manufacturing processed of invention product, and security is higher.
Mg-Zr alloys in invention product, has precedence over carbon element and the effect that stops carbon element oxidation is played in oxidizing substance reaction.After the Mg-Zr alloys of invention interiors of products is heated, magnesium steam raising is to the hot side of invention product, with together with the Mg-Zr alloys of hot side and O
2, CO
2, the reaction of the oxidizing substance such as CO, FeO, generate magnesium oxide tight zone.The generation of magnesium oxide tight zone is conducive to improve invention product in the density of hot side, can improve the resistance to fouling of slag and permeability resistance, 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 Mg-Zr alloys
2.Zirconium white is a kind of high grade refractory.Zirconium white with monoclinic phase appearance, becomes Tetragonal to 1100 ℃ of left/right rotations in temperature-rise period at normal temperatures, 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 and follow larger volumetric expansion in the time of cooling.The reversible transformation that zirconium white has causes it in certain temperature range internal volume, with temperature, to improve and shrink, and with temperature, reduces and expands.This and the contrary behavior of thermal expansion other material, easily causes and contain cracking of zirconic goods when heating up or lowering the temperature for about 1000 ℃.Zirconium white, when being changed to monoclinic phase by Tetragonal (martensitic transformation), is followed volume and change in shape, can absorb 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 contributes to the reduction of the coefficient of thermal expansion of refractory product integral body.Due to ZrO
2the heat-shock resistance that has 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 anhydrous binder for refractory material.Wherein novolac resin liquid bonding agent need add 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 packs magnesium oxide, calcium oxide raw material fine powder in mixing machine into and mixes together with Mg-Zr alloys powder, obtains pre-mixing fine powder;
(2) preparation of pug: magnesium oxide, calcium oxide raw material particle are added in mixing machine, add binding agent for carbonic refractory material, carbon element and step (1) gained pre-mixing fine powder to continue to mix, obtain pug after mixing;
(3) moulding: step (2) gained pug is weighed, add in mould and use pressing machine extrusion forming, obtain adobe; Gained adobe is put into kiln road and be heated to 120 ~ 330 ℃, toast 5 ~ 25h;
(4) packing: by the cooling rear waterproof packing of step (3) gained adobe, obtain 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 packs magnesium oxide, calcium oxide raw material fine powder in mixing machine into and mixes together with Mg-Zr alloys powder, obtains pre-mixing fine powder; In connection with 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 mixing machine, add bonding agent, carbon element, the pre-mixing fine powder of step (1) gained to continue to mix, obtain pug after mixing;
(3) moulding: step (2) gained pug is weighed, add in mould and use pressing machine extrusion forming, obtain adobe;
(4) baking: portioned product need to be put into gained adobe in kiln road and be heated to 300 ~ 450 ℃, is incubated 3 ~ 20h;
(5) packing: by step (3), the cooling rear waterproof packing of (4) gained adobe, obtain product mg-ca-carbon refractory.
Beneficial effect of the present invention: the magnesium-calcium-carbon refractory materials that adopts the technology of the present invention to prepare, taken into account oxidation-resistance, high thermal resistance, anti-slag penetration, heat-shock resistance and produceability.
Embodiment
Content in following embodiment is parts by weight.
Embodiment 1
Mg-ca-carbon refractory by weight proportioning is as follows :-198 10 parts, graphite, 15 parts of needle cokes, 64 parts of dolomite sands, 6 parts, Mg-Zr alloys powder, 4.5 parts of the liquid phenolic resins of moisture < 0.5%, 0.5 part of urotropine.Wherein in Mg-Zr alloys powder, zirconium content is 10%, 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 are added in mixing machine and mix 20min, obtain pre-mixing fine powder;
(2) preparation of pug: dolomite sand particle and urotropine are added in mixing machine and mixed, then add liquid phenolic resin to mix 5 minutes, add needle coke and graphite to continue to mix 15 minutes; Add again step (1) gained pre-mixing fine powder, mix after 10 minutes and obtain pug;
(3) moulding: step (2) gained pug is weighed, add in mould and use pressing machine extrusion forming, obtain adobe; By adobe baking, top temperature is 200 ℃, toasts 10 hours;
(4) packing: by the cooling rear waterproof packing of step (3) gained adobe, obtain product mg-ca-carbon refractory.
This product sample is pressed the oxidation-resistance that GB/T13244 detects 1000 ℃ * 3h, and 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 the test follower head of 15 times and breaks.This product is 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 :-194 2 parts, graphite, and 1 part of N220 carbon black, 80 parts of dolomite sands, 12 parts, magnesia, 3 parts, Mg-Zr alloys powder, 2 parts, coal tar, wherein in Mg-Zr alloys powder, zirconium content is 3%, granularity is for being 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 magnesia powder that granularity is less than to 0.074mm packs in premixer and mixes 10 minutes together with Mg-Zr alloys, obtains pre-mixing fine powder; Coal tar thermal dehydration, to moisture < 0.3%, and insulation makes it keep liquid.
(2) preparation of pug: will add in mixing machine and mix after the heating of dolomite sand particle, then add hot tar to mix 2 minutes, add-194 graphite to mix 2 minutes, add carbon black to continue to mix 2 minutes, then add the mixing of step (1) gained pre-mixing fine powder within 10 minutes, to obtain pug.
(3) moulding: step (2) gained pug is weighed while hot, add in mould and use pressing machine extrusion forming, obtain adobe.
(4) packing: by the cooling rear waterproof packing of step (3) gained adobe, obtain product mg-ca-carbon refractory.
This product sample is pressed the oxidation-resistance that GB/T13244 detects 1000 ℃ * 3h, and 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 the test of 7 times and not occur crackle.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, Mg-Zr alloys powder, 2.8 parts of mid-temperature pitches, wherein in Mg-Zr alloys, the ratio of zirconium is 35%, granularity is≤10 microns.
(1) preparation of pre-mixing fine powder: the fine powder of granularity≤0.1mm in calcium magnesia sand, dolomite sand and Mg-Zr alloys powder are added in premixer, be pre-mixed evenly, obtain pre-mixing fine powder;
(2) preparation of pug: to 160 ℃, insulation is to emerging without steam by mid-temperature pitch heating liquefaction, and moisture content < 0.2%; The dolomite sand that is 6-0.1mm by granularity and calcium magnesia sand particle are heated to 200 ℃ and send in mixing machine and mix, and pour pitch liquation mixings 2min into after mixing 1min, add N220 carbon black to stir 2min, then add step (1) gained pre-mixing fine powder mixing 15 minutes; Mix and to finish rear pug to be put into insulated tank;
(3) moulding: step (2) gained pug is weighed, after add extrusion forming in 1000 tons of friction press stock moulds, obtain adobe; The adobe of gained is put into kiln road and be heated to 320 ℃ ± 10 ℃, be incubated 5 hours, kiln discharge;
(4) packing: by the cooling rear waterproof packing of step (3) gained adobe, obtain product mg-ca-carbon refractory.
This product sample is pressed the oxidation-resistance that GB/T13244 detects 1000 ℃ * 3h, and 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 the test of 5 times and not occur crackle.This product, for RH stove lower channel place, can substitute poisonous magnesia chrome brick.
Claims (1)
1. a mg-ca-carbon refractory, is characterized in that described 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;
The granularity of described Mg-Zr alloys is less than or equal to 0.25mm; In Mg-Zr alloys, zirconium content is 3% ~ 35%, and all the other are magnesium and impurity; Mg-Zr alloys is powdery;
Described carbon element is one or more in graphite, carbon black and needle coke;
Described magnesium oxide, calcium oxide raw material are one or both in calcium magnesia sand or dolomite sand, or the mixture of one or both and magnesia in calcium magnesia sand or dolomite sand; Described magnesium oxide, calcium oxide raw material are divided into particle and fine powder;
Described binding agent for carbonic refractory material is one or more in the mixture of pitch liquation, tar liquid, novolac resin liquid and urotropine;
Content >=2.5% of CaO in described mg-ca-carbon refractory.
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| CN201210400111.2A CN102910917B (en) | 2012-10-20 | 2012-10-20 | Magnesium-calcium-carbon refractory material |
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| CN201210400111.2A CN102910917B (en) | 2012-10-20 | 2012-10-20 | Magnesium-calcium-carbon refractory material |
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| 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 |
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| CN100560538C (en) * | 2007-10-18 | 2009-11-18 | 武汉科技大学 | A kind of ZrO that contains 2Magnesia carbon brick and preparation method thereof |
| CN102276271A (en) * | 2011-06-29 | 2011-12-14 | 江苏苏嘉集团新材料有限公司 | Preparation method of normal temperature solidified magnesium carbon brick |
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