CN102924097A - Carbon titanium combining self-protection brick for blast furnace hearth and furnace bottom - Google Patents
Carbon titanium combining self-protection brick for blast furnace hearth and furnace bottom Download PDFInfo
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- CN102924097A CN102924097A CN201210435107XA CN201210435107A CN102924097A CN 102924097 A CN102924097 A CN 102924097A CN 201210435107X A CN201210435107X A CN 201210435107XA CN 201210435107 A CN201210435107 A CN 201210435107A CN 102924097 A CN102924097 A CN 102924097A
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Abstract
The invention discloses a carbon titanium combining self-protection brick for a blast furnace hearth and a furnace bottom. By special ingredient proportioning, the carbon titanium combining self-protection brick has micropores and high thermal conductivity of microporous carbon bricks, molten iron corrosion resistance anti-scouring performance of a ceramic cup material and the effects of a titanium ore protecting furnace, can solve the problems that the blast furnace hearth is burnt through frequently in recent years and the furnace bottom is too high in warming speed and short in service life, and is expected to become a substitute product for a carbon brick for a blast furnace.
Description
Technical field
The present invention relates to a kind of refractory materials for blast furnace hearth, furnace bottom.
Background technology
Iron-smelting blast furnace cupola well, furnace bottom are abominable with the refractory materials working condition, the life-span weak point is one of weak link that affects the blast furnace whole service life.The refractory materials that existing blast furnace hearth, furnace bottom are used and structure are divided two large classes basically: the one, and micropore and ultramicropore carbon line, the one, oxide ceramics cup and brick fuel compound Lining.
The advantage of micropore and ultramicropore brick fuel is that the carbon materials difficulty is wetting, the difficult infiltration of slag iron, thermal conduction good (thermal conductivity 13-30W/mk).It can coagulate altogether thermoisopleth (1150 ℃) to slag iron and be pushed in the stove; that is, the place that contacts with molten iron in the stove on the surface of brick fuel forms the solid-state protective film of one deck, and this rete is that slag iron forms slag crust in the brick fuel surface solidification; protect brick fuel, reach the purpose of blast furnace longevity.But because of reasons such as blast furnace operating and the operations of tapping a blast furnace, the less stable of slag crust, fragile slag crust is in a single day destroyed, and brick fuel just directly contacts with molten iron.The molten iron corrode index of brick fuel is up to 25%-30%; Because of the solubleness of carbon in molten iron of brick fuel higher, caused the chemical erosion of brick fuel, lower (the cold crushing strength≤50MPa) of the intensity of brick fuel, the scouring capability of high temperature resistance molten iron and slag is relatively poor, particularly during blast furnace casting, the molten iron of high temperature and slag form circulation, cause the cupola well brick fuel to form " shape of a hoof " erosion state.The alkali resistant of brick fuel (K and Na) property is more excellent, but alkali vapor gos deep into the inner somewhere (this place's temperature reaches 800 ℃-870 ℃) of brick fuel by each crackle of pore of brick fuel, the reaction of alkali and carbon makes the brick fuel embrittlement and ftractures, cause cupola well brick fuel masonry to form ring shake, reduced the thermal conductivity of brick fuel, be unfavorable for the formation of slag crust, then accelerated the damage of brick fuel.The oxidation-resistance of brick fuel is relatively poor, has also accelerated its rate of decay.
Oxide ceramics cup material is mainly oxide refractories (such as the corundum-mullite brick, low cement corundum pouring material prefabricated section, composite brown corundum brick, Plastic phase bonded corundum brick and microporous corundum brick).Its poor thermal conductivity, good heat preservation performance can push away the alkalization encroachment line of 1150 ℃ of slag iron lines of solidification and 800-870 ℃ in stove and stays in the ceramic cup, forms slag crust protection brick fuel and also reduces alkali to the erosion of brick fuel.The oxide ceramics cup strength of materials is high, and (cold crushing strength 〉=100MPa), erosion resistibility is strong; Its molten iron corrode index is very low, does not also have problem of oxidation.But the ceramic cup brick scarcely is micropore or ultramicropore brick, and slag iron and alkaloids infiltrate brick body inside by pore, reduced the fire performance (melting point depression) of brick, be subject to chemical erosion, the original structure of brick is destroyed, intensity significantly reduces, and erosion resistibility also decreases.Facts have proved that existing ceramic cup be difficult to be judged its work-ing life accurately.The application initial stage it blast furnace hearth, furnace bottom brick fuel have been played provide protection, still, the intermediary and later stages of blast furnace still will keep by brick fuel, therefore also difficult realize long-lived.
Summary of the invention
The invention discloses and a kind ofly can overcome simultaneously the blast furnace hearth of the shortcoming of above-mentioned brick body, the brick that furnace bottom is used in conjunction with above-mentioned two kinds of existing brick body advantages, purpose is to substitute current blast furnace hearth, brick fuel that furnace bottom is commonly used.
The present invention selects by special composition proportion and material, and processes under certain processing condition.
The present invention adopts the material of following granular size and composition proportion to be mixed and processed:
Material composition explanation and function analysis:
(1) high aluminium material: be one or more compound uses of brown corundum, fused corundom, alundum, bauxite chamotte.Particularly brown corundum and bauxite chamotte, its Al2O3 content is high, and foreign matter content is few, and refractoriness is high, and corundum content is high, hardness is wear-resisting greatly, and contains a certain amount of TiO2(3-5%), a small amount of titanium source is provided.
(2) carbon raw: described carbon materials is one or more compound uses of crystalline flake graphite, synthetic graphite, Electrically calcined anthracite, coke, carbon black, pitch, resin.Particularly the crystalline flake graphite heat-conductivity conducting is good, and slag and molten iron are poor to its wettability, and chemical resistance of concrete is good, and Young's modulus is low, and good thermal shock stability, resistance of oxidation are better than other carbon materialses (the carbon materials weak point is that oxidation-resistance is poor).
(3) metal powder: metal powder is one or more compound uses of Si, Al, Mg, Zn, Ti and alloy thereof, the avidity of itself and oxygen is higher than carbon materials, can prevent the oxidation of carbon materials, and can react the Formed compound (such as β-SiC), nitride with carbon materials, fill and stop up pore, function with microporous, the intensity (normal temperature and hot strength) that simultaneously oxide compound and non-oxidized substance particle is combined and improved goods.
(4) nonmetallic compound powder is SiC, Si
3N
4, BN, B
4One or more compound uses of C, CaB, ZrB.SiC particularly has the effect of antioxidant as metal additive, its hardness high abrasion, and not wetting by molten iron and slag, slag resistance is good, alkali-resistivity (K
2O, Na
2O) fine, SiC is good electro-conductive material, also is good thermally conductive material, improves the thermal conductivity of brick.
(5) titaniferous materials: furnace retaining material (titanium source), described titaniferous materials is Ti, TiO
2, ilmenite concentrate, TiC, TiN, Ti(C, N) etc. one or several.Ti solubleness in molten iron is very low easily to be separated out, and and C.N; TiO
2In goods manufacturing or use procedure, generate Ti(C, N), can improve the viscosity of slag, solidify the formation slag crust, play the effect of furnace retaining.
(6) carbon black: carbon element is provided, promotes the reaction with metal, the filling pore can change the structure after the resin coking.
(7) hard pitch powder: carbon element is provided, promotes the reaction with metal, the filling pore can change the structure after the resin coking.
(8) phenol-formaldehyde resin powder and liquid phenolic resin wedding agent provide carbon element.
After above-mentioned raw materials is ready to, adopt following technique to be made into carbon titanium base in conjunction with the self preservation brick:
1, pug preparation
Edge runner-wet mill, order of addition(of ingredients): thick, the middle particle of (1) high aluminium material; (2) liquid resin; (3) premixed powder (being the mixture of other surplus materialss); (4) pug (being the mixture that forms after above-mentioned three steps); (5) Sleepy material (be about to pug and place for some time).
2, moulding and thermal treatment
Moulding is heat-treated under 200-250 ℃ of condition with high tonnage friction or hydraulic press moulding, the adobe after the moulding.
3, burn till
Under protective atmosphere, burn till (reducing atmosphere or nitrogen atmosphere), firing temperature 1350-1550 ℃, firing time: more than 8 hours.
4, oil immersion and coking are processed
Brick after burning till carries out coking at 〉=500 ℃ and processes through vacuum pressed oil immersion or dipping (use tar-bitumen) afterwards.
5, processing and combination
Brick after dipping or coking are processed carries out mechanical workout and pre-the block.
Carbon titanium base disclosed by the invention is the anti-molten iron erosion that high thermal conductivity, the stupalith of carbon materials is good and Ti(C, the N of titanium ore furnace retaining technology in conjunction with the self preservation brick) trinity integrates.
This project development carbon titanium base has four characteristics in conjunction with the self preservation brick:
The one, micropore (mean pore size≤0.5 μ m, aperture≤1 μ m pore volume 〉=85%), the same with the ultramicropore brick fuel with micropore, the air vent aperture miniaturization, the aperture is little, and the difficult infiltration of slag iron and alkali has reduced the reduction of chemical erosion and structure;
The 2nd, good heat conductivity (〉=14W/mk), the same heat conductivity with brick fuel is good, can cooperate with water cooling wall heat is spread out of, and 1150 ℃ of slag iron is solidified thermoisopleth shift onto in the stove, forms the slag crust protection on the surface of brick;
The 3rd, anti-molten iron erosion≤0.5% is the same with corundum-mullite brick as the microporous corundum brick composite brown corundum brick;
The 4th, have the effect of titanium ore furnace retaining, be one of current blast furnace hearth, the long-lived effective means of furnace bottom with the titanium ore furnace retaining.Usually, have in sintered iron ore with addition of the ilmenite concentrate fettling, have at tuyere injection and contain ilmenite concentrate coal dust fettling, also have in the air port and to feed titanium oxide silk fettling, its principle is under the blast furnace production status, and titanium-containing compound has generated dystectic Ti(C, N), improved viscosity coefficient of dross, solidified and cover on the brick with scum.Be added with titaniferous materials in this Product Process, original position has formed Ti(C, N), play the effect of on the spot furnace retaining and the effect of " autoprotection ".
The invention discloses the kind of metal additive and quantity to impact and the microporous mechanism of carbon titanium base in conjunction with self preservation brick micropore; The adding form and the quantity that disclose graphite are machine-processed in conjunction with impact and the heat conduction of self preservation brick thermal conductivity on carbon titanium base, and the adding form of silicon carbide and quantity are on the impact of carbon titanium base in conjunction with self preservation brick thermal conductivity; The kind of titanium-containing compound and add-on are disclosed to Ti(C, N) impact that forms; Disclose various starting material and manufacturing condition to carbon titanium base in conjunction with self preservation brick micropore, thermal conductivity and Ti(C, N) formation condition affect rule.
1, microporous mechanism
In carbon containing refractory, add metal Si and will have following two reactions:
(1) Si and C direct reaction, metal Si mainly generate β-SiC with the wedding agent charcoal that contacts and the reaction of graphite arris;
(2) generate β-SiC by mass transferring in gas phase, at first CO reaction in Si and the pore:
Si（s）+CO（g）=SiO（g）+C（s）
The SiO gas that generates reacts below upper generation of the higher carbonaceous point of activity by gas phase diffusion:
SiO（g）+2C（s）=SiC（s）+CO（g）
Carbon titanium base is shown in Fig. 1, Fig. 2, shown in Figure 3 in conjunction with the microstructure scanning electron microscope picture of self preservation brick, can prove that by this picture metal Si reaction generates β-SiC.
If in carbon containing refractory, add metal A l.Al
4C
3It is apparent that by gas phase to generate, because the Al that the microstructure scanning electron microscopic observation of brick generates
4C
3Be the whisker of growing in pore, photo is shown in Fig. 4, Fig. 5.
Al
4C
3The process that generates may be that at first the reaction of the CO in Al and the pore generates Al
2O gas:
2Al（l）+CO（g）=Al
2O（g）+C（s）
According to New phase formation principle, Al
2O and CO have generated cenotype Al in solid phase or the reaction of liquid phase surface
4C
3:
2Al
2O（g）+8CO（g）=Al
4C
3+5CO
2
In the carbon containing refractory that is added with metal A l, add metal M g or MgAl alloy, because of the temperature that liquid phase occurs lower (436 ℃), metal M g has promoted Al
4C
3Formation reaction:
2Mg
3Al
2+2C=Al
4C
3+6Mg
2Mg
3Al
2+3CO=Al
4C
3+6MgO
2Mg
3Al
3+6CO=Al
4C
3+6MgO+3C
The microstructure stereoscan photograph that adds the brick of Mg is shown in Fig. 6.
β-SiC and Al
4C
3Generation stopped up pore in the brick, make the aperture miniaturization.
2, the principle of heat conduction
Graphite is the good conductor of electricity, also is the good conductor of heat.Graphite is added to fine powder form in the matrix of brick, after the add-on of graphite reaches some amount, flaky graphite in matrix mutually overlap joint consisted of continuous conductor, insert in the athermanous stupalith just as one by one " wire ", be illustrated in Fig. 7.
Carbon titanium base is shown in Fig. 8 in conjunction with the microstructure stereoscan photograph of self preservation brick.
3, titanium carbonitride synthesis technique mechanism
Titanium carbide is black powder, and its fusing point is high, have high temperature oxidation resisting, intensity is high, hardness is high, thermal conductivity good, good toughness, to the excellent properties such as unreactiveness of iron and steel metalloid, be wear-resisting, the refractory materials that the utmost point has using value.
Titanium nitride is golden yellow, its fusing point is high, hardness is high, good with metal profit warm nature, self-lubricating function, stable chemical performance, acid and alkali-resistance are arranged, also be wear-resisting, refractory materials that the utmost point has using value.
Titanium carbide and titanium nitride synthetic method are a lot, and titanium carbide and titanium nitride also can form continuous Solid solution.TiO among the present invention
2The hot nitrogenizing reaction of carbon synthesizes Ti(C, N):
2TiO
2（s）+6C（s）+N2（g）=2Ti（C,N）（s）+4CO（g）
Ti(C, N) sosoloid improved viscosity coefficient of dross, solidify and cover on the brick with scum, played the on the spot effect of protection tile body and body of heater.
Description of drawings
Fig. 1. the granular SiC microstructure scanning electron microscope (SEM) photograph in the brick on the graphite edge
Fig. 2. the β that disperse distributes in the brick-SiC microstructure scanning electron microscope (SEM) photograph
Fig. 3. the granular β of 0.1～0.3 μ m in the brick-SiC microstructure scanning electron microscope (SEM) photograph
Fig. 4. the fibrous Al that grows in the pore on the aluminum particulate in the brick
4C
3The microstructure scanning electron microscope (SEM) photograph
Fig. 5. the needle-like Al that grows in the pore in the brick
4C
3The microstructure scanning electron microscope (SEM) photograph
Fig. 6. carbon titanium base is in conjunction with the tabular and staple fibre shape Al in the self preservation brick
4C
3
Fig. 7. carbon titanium base is in conjunction with the heat conduction principle of self preservation brick
Fig. 8. the contiguous network structure photo that carbon titanium base forms in conjunction with graphite in the self preservation brick
Embodiment
Embodiment 1:
Embodiment 2:
Its product and ceramic cup material and brick fuel performance index contrast both at home and abroad:
Can draw this product by above contrast and have four large characteristics: (1) micropore, mean pore size≤0.10 μ m ,≤1 μ m pore volume 〉=85% is the same with microporous corundum brick with the ultramicropore brick fuel; (2) heat conduction, 600 ℃ of heat conduction 〉=14W/mK are the same with the ultramicropore brick fuel as microporous carbon brick; (3) anti-molten iron erosion≤0.5% is the same with composite brown corundum brick as microporous corundum brick; (4) has the function of titanium ore furnace retaining, TiO
2Generate Ti (C.N) in 〉=5% brick.Therefore, this product can substitute existing brick fuel as the liner of cupola well, furnace bottom.
Claims (7)
1. a cupola well, furnace bottom in conjunction with the self preservation brick, is characterized in that described self preservation brick includes following raw material with carbon titanium base, and its granular size and weight ratio are:
Add the liquid phenolic resin of 3.5-4% of above-mentioned substance total mass as wedding agent.
2. self preservation brick as claimed in claim 1 is characterized in that described high aluminium material is one or more compound uses of brown corundum, fused corundom, alundum, bauxite chamotte.
3. self preservation brick as claimed in claim 2 is characterized in that described carbon materials is one or more compound uses of crystalline flake graphite, synthetic graphite, Electrically calcined anthracite, coke, carbon black, pitch, resin.
4. self preservation brick as claimed in claim 3 is characterized in that described nonmetallic compound powder is SiC, Si
3N
4, BN, B
4One or more compound uses of C, CaB, ZrB.
5. self preservation brick as claimed in claim 4 is characterized in that described metal powder is one or more compound uses of Si, Al, Mg, Zn, Ti and alloy thereof.
6. self preservation brick as claimed in claim 5 is characterized in that described titaniferous materials is Ti, TiO
2, ilmenite concentrate, TiC, TiN, Ti(C, N) etc. one or several.
7. such as the self preservation brick of claim 1 or 6, it is characterized in that the production technique of this self preservation brick is:
The preparation of A pug
Edge runner-wet mill, order of addition(of ingredients): thick, the middle particle of (1) high aluminium material; (2) liquid resin; (3) premixed powder; (4) pug; (5) Sleepy material;
B moulding and thermal treatment
Moulding is heat-treated under 200-250 ℃ of condition with high tonnage friction or hydraulic press moulding, the adobe after the moulding;
C burns till
Under protective atmosphere, burn till (reducing atmosphere or nitrogen atmosphere), firing temperature 1350-1550 ℃, firing time: more than 8 hours;
D oil immersion and coking are processed
Brick after burning till carries out coking at 〉=500 ℃ and processes after vacuum pressed oil (tar-bitumen) soaks or floods;
E processing and combination
Behind the dipping or the brick of coking after processing carry out mechanical workout and pre-the block.
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| CN106316423A (en) * | 2016-08-19 | 2017-01-11 | 武汉科技大学 | Refractory castable for lining of thermal equipment and using method of refractory castable |
| CN107721447A (en) * | 2017-11-29 | 2018-02-23 | 鲁山县方圆工程技术有限公司 | Ferronickel electric furnace chromium-aluminium spinel brick fuel and preparation method thereof |
| CN107903039A (en) * | 2017-11-29 | 2018-04-13 | 鲁山县方圆工程技术有限公司 | A kind of magnesium composite brick for ferronickel electric furnace and preparation method thereof |
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| CN107903039A (en) * | 2017-11-29 | 2018-04-13 | 鲁山县方圆工程技术有限公司 | A kind of magnesium composite brick for ferronickel electric furnace and preparation method thereof |
| CN108002379A (en) * | 2017-12-15 | 2018-05-08 | 吉林市松江炭素有限责任公司 | A kind of method for increasing carbon black and recycling number |
| CN112028653A (en) * | 2020-09-11 | 2020-12-04 | 武汉钢铁有限公司 | High-thermal-conductivity and corrosion-resistant self-protecting carbon brick for blast furnace and preparation method thereof |
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