CN102653471A - Method for producing magnesium carbon brick by using boron magnesium ore as additive - Google Patents
Method for producing magnesium carbon brick by using boron magnesium ore as additive Download PDFInfo
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- CN102653471A CN102653471A CN2011100495015A CN201110049501A CN102653471A CN 102653471 A CN102653471 A CN 102653471A CN 2011100495015 A CN2011100495015 A CN 2011100495015A CN 201110049501 A CN201110049501 A CN 201110049501A CN 102653471 A CN102653471 A CN 102653471A
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- additive
- magnesium ore
- powder
- boron magnesium
- ore deposit
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Abstract
The invention discloses a method for producing a magnesium carbon brick by using boron magnesium ore as an additive, which enhances the oxidation resistance, permeation resistance and high temperature corrosion resistance of the magnesium carbon brick. Fused magnesite and crystalline flake graphite with different particle sizes are used as raw materials; phenol formaldehyde resin and solid asphalt powder are used as binders; and boron magnesium ore or boron magnesium ore+Al powder are used as an additive. The method comprises the following steps: proportioning, thoroughly mixing, forming by a hydraulic press, and carrying out high temperature treatment to obtain the magnesium carbon brick. The additive boron magnesium ore adopted by the invention has the advantages of accessible raw material and low cost; by using the natural boron magnesium ore as the novel additive, the invention can enhance the high temperature properties and oxidation resistance of the magnesium carbon brick, solves the problems of high price and complex production technique in the current boron-containing additive, and can effectively utilize the natural boron magnesium ore resources, thereby lowering the production cost of the magnesium carbon brick and saving the energy.
Description
Technical field
The present invention relates to produce the method for magnesia carbon brick, particularly a kind of method of making the Additive Production magnesia carbon brick of boron magnesium ore deposit.
Background technology
Magnesia carbon brick has excellent resistance to slag corrosion, comparatively ideal thermal shock resistance, and heat conductivity and dense structure's property are widely used on steel-making converter, electric furnace and ladle refining furnace and the ladle slag line.Yet carbon has the weakness of easy oxidation, is easy to cause that product strength reduces, and corrosion resistance descends, and magnesia carbon brick is lost ground.In magnesia carbon brick, add additive and can prevent oxidation of coal effectively, and help improving the high temperature use properties of refractory materials.The effect of additive is divided into two aspects: be from the thermodynamics angle on the one hand; Promptly under working temperature; The resultant of additive or additive and carbon reaction is bigger than the avidity of carbon and oxygen with the avidity of oxygen, have precedence over oxidized, thereby play the effect of protecting carbon; Be that driven angle of mechanics is considered on the other hand, additive and O
2, the compound that generates of CO or C reaction can change the microstructure of material, as increasing density, stops up pore, hinders O
2And the diffusion of reaction product etc.
At present, common magnesia carbon brick additive mainly contains two types: the metal or alloy fine powder; Nonmetal fine powder.
The lemel that adds mainly contains Al, Si, Mg, Ca etc., and wherein Al, Si are the most common.In heat treatment process, Al and Si can react in material, and wherein, Al is reduced into C (s) to CO (g), and generate Al
2O
3, playing the effect of inhibited oxidation, reaction formula is following:
2Al
(l)+3CO
(g)→Al
2O
3(s)+3C
(s)
And this process is accompanied by certain volumetric expansion, causes the densification of materials microstructure, therefore can suppress the oxidation of carbon;
Si at first reacts in material:
Si
(s)+C
(s)+O
2(g)＝S
iO
(g)+CO
(g)
Then, the CO of reaction generation can make SiO (g) further be oxidized to SiO again
2:
S
iO
(g)+CO
(g)＝S
iO
2(g)+C
(s)
Therefore, the anti-oxidation mechanism of additive A l and Si: on the one hand be the apparent porosity that thing phase change that Al, Si take place in heat treatment process has reduced material, make the material structure densification, thereby reduced oxidizing gas (like O
2) amass with effective contact of material; On the other hand, Al, Si react the Al that discharges
2O, SiO gas are met O
2Or CO gas can react the solid-state Al of generation
2O
3And SiO
2, be deposited on the solid surface in the pore, block pore, suppress the diffusion of gas, thereby played anti-oxidation effect.
Yet, it should be noted that metal A l can generate Al with the C reaction more than 1000 ℃
4C
3, and Al
4C
3Can and react from the water vapour in the environment:
Al
4C
3+12H
2O＝3CH
4+4Al(OH)
3
Follow bigger volumetric expansion, thereby to the destruction of material production potential.
The alloy fine powder that adds mainly contains binary or ternary alloys such as Al-Si, Al-Mg, Al-Mg-Ca, Si-Mg-Ca, Al-Si, the Al-Mg alloy of mainly containing commonly used.
The nonmetal fine powder that adds mainly contains boron-containing additive and silicon-containing additive.Silicon-containing additive has SiC, Si
3N
4(only considering the β type) etc.Boron-containing additive mainly contains norbide (B
4C), six calcium boride (CaB
6), TiB2 (TiB
2), zirconium diboride (ZrB
2) etc.
The Chinese patent publication number is CN1237562; " inhibitor of carbon containing refractory " discloses a kind of inhibitor of carbon containing refractory; By at least a composition the in the zinc powder of weight percentage 0.15～10% or zinc powder and aluminium, magnesium, silicon, silicon calcium powder, silit, norbide, magnesium aluminum-alloy powder, the silicon nitride powder; Zinc powder >=0.15% wherein, granularity is less than 0.5mm.This inhibitor is the formation of inhibited oxidation Decarburized layer effectively, can improve the oxidation-resistance of refractory materialss such as magnesia carbon brick.
Above-mentioned magnesia carbon brick additive, the antioxidant effect that has is not ideal; Though what have has improved the magnesia carbon brick oxidation-resistance, other high-temperature behaviors have received influence; The boron-containing additive oxidation-protective effect is good, but because its expensive price and complicated manufacturing process have limited their application and popularization.
Summary of the invention
The invention provides and a kind ofly do the method for Additive Production magnesia carbon brick, both improved the oxidation-resistance of magnesia carbon brick, strengthened its permeability resistance, high temperature resistance aggressiveness again with boron magnesium ore deposit.
The method of doing the Additive Production magnesia carbon brick with boron magnesium ore deposit provided by the invention may further comprise the steps:
A. material is selected
Adopting electrosmelted magnesite clinker, the crystalline flake graphite of different-grain diameter is raw material; Adopt resol and solid bitumen powder as wedding agent; Adopt boron magnesium ore deposit or boron magnesium ore deposit+Al powder as additive;
B. prepare burden
Get electrosmelted magnesite clinker, crystalline flake graphite, the resol batching of different-grain diameter.Its weight percent set of dispense is such as following:
Particle diameter 3～1mm electrosmelted magnesite clinker 45～55%
Particle diameter＜1mm electrosmelted magnesite clinker 15～25%
Particle diameter＜0.088mm electrosmelted magnesite clinker 15～20%
Crystalline flake graphite 5～15%
Resol 2～4%
C. add pitch and additive
Gross weight with above-mentioned batching is 100%, the pitch of added weight per-cent 0.5～2%; The boron magnesium ore deposit of weight percent 0.5～6% or boron magnesium ore deposit+Al powder, additive boron magnesium ore deposit wherein are through 800～1000 ℃ of roastings and are incubated 1h, are crushed to the powder below 100 orders after the roasting; The mass ratio of boron magnesium ore deposit+Al powder wherein is boron magnesium ore deposit: Al powder=2: 1.
D. batch mixing moulding
According to said ratio; In magnesia particle, add wedding agent resol; Add the mixing fine powders of the crystalline flake graphite, additive boron magnesium ore deposit or boron magnesium ore deposit+Al powder, wedding agent asphalt powder and the magnesia powder that are pre-mixed after mixing, behind the thorough mixing, use the hydropress moulding; Forming pressure is 500Mpa, pressurize 1min.The adobe of forming is handled through 200 ℃ * 10h again, processes magnesia carbon brick.
The present invention compared with prior art its obvious improvement is embodied in outstanding beneficial effect:
Boron magnesium ore deposit at high temperature forms the liquid film that is covered on the crystal grain as additive, successive second a phase thin film netowrk on crystal boundary, occurs, has effectively stoped the oxidation of carbon.The borate liquid phase Mg that promptly generates
3B
2O
6Therefore wettability to graphite is poor, but good to the MgO wettability, and the protection to carbon is not because carbon is wrapped, but the boric acid salt face is wrapped in around the MgO particle, thereby has stoped O to contact with C, reaches the effect of protecting C.The O here derives from the oxide compound and the airborne O of iron in the slag
2, CO
2, SiO
2Deng, and be dissolved in the MgO among the molten steel or in the brick.
Boron magnesium ore deposit raw material be easy to get and cost low; Use natural boron magnesium ore deposit as new additive agent, not only can improve the high-temperature behavior and the resistance of oxidation of magnesia carbon brick, and solved current boron-containing additive and cost an arm and a leg; The problem of complex manufacturing; And can effectively utilize natural boron magnesium ore resources, reduce the magnesia carbon brick production cost, save energy.
Embodiment
Embodiment 1
Present embodiment adds boron magnesium ore deposit as additive, and each weight percentages of components is following:
Particle diameter 3～1mm electrosmelted magnesite clinker 50%
Particle diameter＜1mm electrosmelted magnesite clinker 20%
Particle diameter＜0.088mm electrosmelted magnesite clinker 17%
Crystalline flake graphite 10%
Resol 3%
Add pitch 1%
Add boron magnesium ore deposit 0.5～6%
According to said ratio; In magnesia particle, add wedding agent resol; The mixing fine powders that adds the crystalline flake graphite, additive boron magnesium ore deposit, wedding agent asphalt powder and the magnesia powder that are pre-mixed after mixing; Additive boron magnesium ore deposit wherein is through 800～1000 ℃ of roastings and is incubated 1h, is crushed to the powder below 100 orders after the roasting.Behind the thorough mixing, use the hydropress moulding, forming pressure is 500Mpa, pressurize 1min.The adobe of forming is handled through 200 ℃ * 10h again, processes magnesia carbon brick.
The magnesia carbon brick physical and chemical performance detected result of present embodiment production sees the following form:
Practical decarburized depth under the magnesia carbon brick different heating condition of present embodiment production sees the following form:
Embodiment 2
Present embodiment adding boron magnesium ore deposit and Al powder are as additive, and each weight percentages of components is following:
Particle diameter 3～1mm electrosmelted magnesite clinker 50%
Particle diameter＜1mm electrosmelted magnesite clinker 20%
Particle diameter＜0.088mm electrosmelted magnesite clinker 17%
Crystalline flake graphite 10%
Resol 3%
Add pitch 1%
Add boron magnesium ore deposit+Al powder 0.5～6%
According to said ratio; In magnesia particle, add wedding agent resol; The mixing fine powders that adds the graphite, additive boron magnesium ore deposit and Al powder, wedding agent asphalt powder and the magnesia powder that are pre-mixed after mixing; Additive boron magnesium ore deposit wherein is through 800～1000 ℃ of roastings and is incubated 1h, is crushed to the powder below 100 orders after the roasting; The mass ratio of boron magnesium ore deposit+Al powder wherein is boron magnesium ore deposit: Al powder=2: 1.Behind the thorough mixing, use the hydropress moulding, forming pressure is 500Mpa, pressurize 1min.The adobe of forming is handled through 200 ℃ * 10h, processes magnesia carbon brick.
The magnesia carbon brick physical and chemical performance detected result of present embodiment production sees the following form:
Practical decarburized depth under the magnesia carbon brick different heating condition of present embodiment production sees the following form:
Claims (1)
1. do the method for Additive Production magnesia carbon brick with boron magnesium ore deposit for one kind, it is characterized in that this method may further comprise the steps:
A. material is selected
Adopting electrosmelted magnesite clinker, the crystalline flake graphite of different-grain diameter is raw material; Adopt resol and solid bitumen powder as wedding agent; Adopt boron magnesium ore deposit or boron magnesium ore deposit+Al powder as additive;
B. prepare burden
Get electrosmelted magnesite clinker, crystalline flake graphite, the resol batching of different-grain diameter, its weight percent set of dispense is such as following:
Particle diameter 3～1mm electrosmelted magnesite clinker 45～55%
Particle diameter＜1mm electrosmelted magnesite clinker 15～25%
Particle diameter＜0.088mm electrosmelted magnesite clinker 15～20%
Crystalline flake graphite 5～15%
Resol 2～4%
C. add pitch and additive
Gross weight with above-mentioned batching is 100%, the pitch of added weight per-cent 0.5～2%; The boron magnesium ore deposit of weight percent 0.5～6% or boron magnesium ore deposit+Al powder, additive boron magnesium ore deposit wherein are through 800～1000 ℃ of roastings and are incubated 1h, are crushed to the powder below 100 orders after the roasting; The mass ratio of boron magnesium ore deposit+Al powder wherein is boron magnesium ore deposit: Al powder=2: 1;
D. batch mixing moulding
According to said ratio, in magnesia particle, add wedding agent resol, mix the mixing fine powders that the back adds the crystalline flake graphite, additive boron magnesium ore deposit or boron magnesium ore deposit+Al powder, wedding agent asphalt powder and the magnesia powder that are pre-mixed; Behind the thorough mixing; Use the hydropress moulding, forming pressure is 500Mpa, pressurize 1min; The adobe of forming is handled through 200 ℃ * 10h again, processes magnesia carbon brick.
Priority Applications (1)
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|---|---|---|---|
| CN2011100495015A CN102653471B (en) | 2011-03-01 | 2011-03-01 | Method for producing magnesium carbon brick by using boron magnesium ore as additive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100495015A CN102653471B (en) | 2011-03-01 | 2011-03-01 | Method for producing magnesium carbon brick by using boron magnesium ore as additive |
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| CN102653471A true CN102653471A (en) | 2012-09-05 |
| CN102653471B CN102653471B (en) | 2013-11-13 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892647A (en) * | 2017-03-22 | 2017-06-27 | 辽宁中镁控股股份有限公司 | A kind of compound magnesia carbon brick and preparation method thereof |
| CN107140950A (en) * | 2017-04-05 | 2017-09-08 | 中国地质大学（北京） | A kind of preparation method of sucrose combination MgO C fire resistant materials |
| CN107459341A (en) * | 2017-07-18 | 2017-12-12 | 海城利尔麦格西塔材料有限公司 | A kind of magnesia carbon brick and production method by the use of paigeite as additive |
| CN108975925A (en) * | 2018-08-09 | 2018-12-11 | 钱兴 | A kind of preparation method of ladle fire resisting air brick |
| CN110550922A (en) * | 2019-09-23 | 2019-12-10 | 武汉科技大学 | Green low-creep MgO-C brick and preparation method thereof |
| CN112979328A (en) * | 2021-02-08 | 2021-06-18 | 东北大学 | Low-carbon magnesia-carbon refractory material and preparation method thereof |
| CN116589288A (en) * | 2023-04-21 | 2023-08-15 | 江苏苏嘉集团新材料有限公司 | Antioxidant magnesia carbon brick |
| CN117362056A (en) * | 2023-12-07 | 2024-01-09 | 山东海泰高温材料有限公司 | Preparation method and application of magnesia carbon brick for steel ladle |
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| CN101186515A (en) * | 2007-12-21 | 2008-05-28 | 杨红 | Ultra-low-carbon steel slag inclusion line magnesium-carbon brick and producing method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892647A (en) * | 2017-03-22 | 2017-06-27 | 辽宁中镁控股股份有限公司 | A kind of compound magnesia carbon brick and preparation method thereof |
| CN107140950A (en) * | 2017-04-05 | 2017-09-08 | 中国地质大学（北京） | A kind of preparation method of sucrose combination MgO C fire resistant materials |
| CN107459341A (en) * | 2017-07-18 | 2017-12-12 | 海城利尔麦格西塔材料有限公司 | A kind of magnesia carbon brick and production method by the use of paigeite as additive |
| CN108975925A (en) * | 2018-08-09 | 2018-12-11 | 钱兴 | A kind of preparation method of ladle fire resisting air brick |
| CN110550922A (en) * | 2019-09-23 | 2019-12-10 | 武汉科技大学 | Green low-creep MgO-C brick and preparation method thereof |
| CN112979328A (en) * | 2021-02-08 | 2021-06-18 | 东北大学 | Low-carbon magnesia-carbon refractory material and preparation method thereof |
| CN116589288A (en) * | 2023-04-21 | 2023-08-15 | 江苏苏嘉集团新材料有限公司 | Antioxidant magnesia carbon brick |
| CN117362056A (en) * | 2023-12-07 | 2024-01-09 | 山东海泰高温材料有限公司 | Preparation method and application of magnesia carbon brick for steel ladle |
| CN117362056B (en) * | 2023-12-07 | 2024-02-20 | 山东海泰高温材料有限公司 | Preparation method and application of magnesia carbon brick for steel ladle |
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| Publication number | Publication date |
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| CN102653471B (en) | 2013-11-13 |
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Inventor after: Qu Dianli Inventor after: Wang Xinjie Inventor after: Guo Yuxiang Inventor after: Zhang Yixian Inventor after: Dai Chenchen Inventor after: Wang Zhixin Inventor before: Qu Dianli Inventor before: Guo Yuxiang Inventor before: Dai Chenchen |
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Effective date of registration: 20161205 Address after: 114044 Anshan province hi tech Zone, thousands of mountain road, No. 185, No. Patentee after: Liaoning Science and Technology Univ. Patentee after: Haicheng Zhongxing High-Grade Magnesia Brick Co., Ltd. Address before: 114044 Anshan province hi tech Zone, thousands of mountain road, No. 185, No. Patentee before: Liaoning Science and Technology Univ. |
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| CP01 | Change in the name or title of a patent holder |
Address after: 114044 Anshan province hi tech Zone, thousands of mountain road, No. 185, No. Co-patentee after: Haicheng Lear MEG Materials Co. Ltd. Sita Patentee after: Liaoning Science and Technology Univ. Address before: 114044 Anshan province hi tech Zone, thousands of mountain road, No. 185, No. Co-patentee before: Haicheng Zhongxing High-Grade Magnesia Brick Co., Ltd. Patentee before: Liaoning Science and Technology Univ. |
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| CP01 | Change in the name or title of a patent holder |