CN102212844B - Carbon metal compound composite material - Google Patents
Carbon metal compound composite material Download PDFInfo
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- CN102212844B CN102212844B CN201010143076.1A CN201010143076A CN102212844B CN 102212844 B CN102212844 B CN 102212844B CN 201010143076 A CN201010143076 A CN 201010143076A CN 102212844 B CN102212844 B CN 102212844B
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- carbon
- metal compound
- composite material
- sic
- compound composite
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Abstract
The invention discloses a carbon metal compound composite material which comprises the following main components: SiC, C, Si3N4 and Si. The preparation method of the carbon metal compound composite material comprises the following steps: (1), weighting, burdening and mixing SiC, C, Si3N4 and Si in proportion, and shaping; (2) nitriding and sintering at the sintering temperature of 1380-1560DEG C for 100-200 hours; (3) dipping in an asphalt impregnation liquid for 8-60 hours; and (4) roasting in nitrogen or storage carbon at 200-1500DEG C for 48-200 hours. By utilizing the carbon metal compound composite material disclosed by the invention, the aluminum liquid flowing state can be effectively improved, and the power consumption of the aluminium refining industry is lowered.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, relate to particularly refractory materials-carbon metal compound composite material that a kind of refining electrolytic bath is used.
The invention still further relates to the preparation method of above-mentioned carbon metal compound composite material.
Technical background
Electrolysis of aluminum is the Main Means of aluminum current metallurgy, the Electrowinning primary aluminum of application aluminum oxide.Electrolyzer adopts carbon anode and carbon cathode conventionally, with villiaumites such as aluminum fluorides, as ionogen, makes Al
2o
3there is electrochemical reaction, O
2molecule and anodic reaction are overflowed, and the aluminium liquid making, after purifying clarification, is cast into aluminium.This process important physical field in aluminium cell has six: potential fields, current field, magnetic field, temperature field (thermal field), velocity field and concentration field.Wherein current field is the energy foundation of electrolyzer operation; Electric current produces magnetic field, and the heat effect of electric current produces thermal field, and the imbalance of Distribution of Magnetic Field causes the motion of ionogen and aluminium liquid, and the motion of ionogen and aluminium liquid causes Al
2o
3diffusion and dissolving with metal; The basis that guarantees that electrolytic process is carried out is not only in the distribution in temperature field, is also the important factor that affects energy balance, and the motion of melt and material diffusion are also exerted an influence.How effectively controlling bath movement is achieved electrolysis, and it is invalid diligent to reduce it, need to adjust the structure in current electrolysis groove and electrolytic process parameter, reach the object that reduces energy consumption, make to smelt at present ton aluminium consumption 14000 degree direct current consumptions and be reduced to 13160 degree, save energy 6% left and right, its meaning is very far-reaching.
Aluminum electrolytic cell bottom negative electrode adopts carbon materials, generally adopts two kinds of semi-graphite carbon cathode and full graphite matter carbon cathodes.
Improving aluminium liquid flow state is the method that reduces power consumption.In ceramic, alternative material is exactly carbonaceous and the large class material of silicon carbide two.
Although but carbonaceous material existing application at present, and obtain certain effect, from long-term safety is used, there is following problem in this material:
(1) carbonaceous material density is little, generally at 1.50-1.80g/cm
3between, with respect to 2.3g/cm
3the aluminium liquid of density, exists and is difficult to the problem of laying in aluminium liquid.In order to solve the problem of laying, only have and negative electrode is made special-shaped, or material is directly fixed on negative electrode, this has brought a series of operational issue to startup of electrolyzer, normal operation.
(2) carbonaceous material intensity is low, and generally at 10-30MPa, for the motion of aluminium liquid melt, material self is subject to very galling, and after the boss that 100mm is high moves 100-120 days, wearing and tearing reach 50% left and right, cannot meet the requirement that generation groove makes 2000 days.
(3) carbonaceous material can only be implemented in overhaul groove.
Summary of the invention
The object of the present invention is to provide a kind of carbon metal compound composite material for refining electrolytic bath.
Another object of the present invention is to provide a kind of method of preparing above-mentioned carbon metal compound composite material.
For achieving the above object, carbon metal compound composite material provided by the invention, its main ingredient is SiC, C, Si
3n
4and Si, wherein SiC accounts for the 50-95% of gross weight, and C accounts for 1-33%, the Si of gross weight
3n
4account for the 1-35% of gross weight, Si accounts for the 0.1-30% of gross weight.
In described carbon metal compound composite material, SiC particle diameter is 3-0 millimeter, and its particle diameter forms and weight ratio is 3-1 millimeter, and: 0.1 millimeter of 1-0.5 millimeter: < is 2-6: 0.1-3.5: 1-5, and C is 0.088-0 millimeter, Si
3n
4for 0.1 millimeter of <, Si is 0.1 millimeter of <.
The method of the above-mentioned carbon metal compound composite material of preparation provided by the invention, its key step is:
1) by SiC, C, Si
3n
4with Si according to the above ratio weigh batching, aftershaping mixes;
2) matrix material of step 1 gained is carried out to nitrogenize and burn till (nitrogen gas purity is 99.99%), temperature is 1380-1560 ℃, and the time is 100-200 hour;
3) matrix material of step 2 gained floods 8-60 hour in bituminizing liquid;
4) infused composite of step 3 gained is at nitrogen (nitrogen gas purity is 99.99%) or 200-1500 ℃ of roasting in burying carbon, and the time is 48-200 hour.
In described method, the nitrogen air speed of step B and step D is than being 1.8-5.5h
-1.
In described method, when step D buries carbon, the weight ratio of fixed carbon and carbon metal compound composite material is 0.3-1.5: 1.
Carbon metal compound composite material of the present invention is when for refining electrolytic bath, except avoiding, the shortcoming of known carbonaceous material, also having following performance:
(1) at 950 ℃ of left and right temperature, do not react with aluminium liquid;
(2), at 950 ℃ of left and right temperature, there is the erosional competency of excellent potential resistance to electrolyte contamination;
(3) volume density is at 3.0g/cm
3above;
At (4) 950 ℃ of left and right temperature, there is excellent refractory body performance of flushing;
(5) there is weak electroconductibility, pollution-free to aluminium liquid.
Embodiment
The present invention is batching according to refractory materials, mixing, moulding, nitrogenize is burnt till and flood, carbon metal compound composite material that the technique such as detection is made.
Concrete operations are, by SiC, C, Si
3n
4with Si respectively according to 50-95%, 1-33%, 1-35% and 0.1-30% weight ratio are carried out weigh batching, through sand mill or the high speed muller 5-40 minute that mixes, the pug having mixed is pressed into adobe on 1000 tons of friction presses or other molding devices, through 150-200 ℃ of temperature, dry within 16-84 hour, (this is known technology, specifically can consult < < fire-proof material technology > >, Wang Weibang chief editor, metallurgical industry press, 1993), after dry, adobe nitrogenize through 100-200 hour at 1380-1560 ℃ of temperature burns till that (air speed of nitrogen is than being 1.8-5.5h
-1), then in bituminizing liquid, flood 8-60 hour, finally at nitrogen, (air speed of nitrogen is than being 1.8-5.5h
-1) or bury 200-1500 ℃ of roasting in carbon, the time is that (while burying carbon, the weight ratio of fixed carbon and carbon metal compound composite material was 0.3-1.5: 1) in 48-200 hour.Can be made into the carbon metal compound composite material of this invention, its performance is as follows:
SiC accounts for the 50-95% of gross weight;
Si
3n
4account for the 1-33% of gross weight;
C accounts for the 1-35% of gross weight;
Void content≤22.8%;
Volume density>=2.47g/cm
3;
Compressive strength >=171MPa;
Folding strength >=18MPa;
High temperature break resistant intensity (1400 * 0.5h ℃) >=23MPa.
Embodiment 1
The Si of 0.1 millimeter of SiC, the C of 224 kilograms of particle diameter 0.088-0 millimeters, the 120 kg particle diameter < of 0.1 millimeter of the SiC of the SiC of 220 kilograms of particle diameter 3-1 millimeters, 44 kilograms of particle diameter 1-0.5 millimeters, 176 kilograms of particle diameter <
3n
4, 0.1 millimeter of 16 kilograms of particle diameter < Si, add in muller, mix 5 minutes, the dextrin that adds 16 kilograms, mixes 5 minutes, then adds 6% water, mix 30 minutes, the pug having mixed is pressed into adobe on 1000 tons of friction presses or other molding devices, through 150 ℃ of temperature dry 84 hours, dry after adobe at 1380 ℃ of temperature, through the nitrogenize of 200 hours, burn till that (air speed of nitrogen is than being 1.8h
-1), then in bituminizing liquid, flood 60 hours, finally at nitrogen, (air speed of nitrogen is than being 1.8h
-1) or bury 200 ℃ of roastings in carbon, the time is 200 hours (while burying carbon, the weight ratio of fixed carbon and carbon metal compound composite material is 0.3: 1).
Its performance is: SiC account for gross weight 53.3%, C account for gross weight 25.1%, Si
3n
4account for gross weight 12.6%, void content 18.2%, volume density 2.75g/cm
3, compressive strength 221MPa, folding strength 38MPa, high temperature break resistant intensity (1400 * 0.5h ℃) 41MPa.
Embodiment 2:
The Si of 0.1 millimeter of the C of the SiC of 0.1 millimeter of the SiC of the SiC of 260 kilograms of particle diameter 3-1 millimeters, 52 kilograms of particle diameter 1-0.5 millimeters, 208 kilograms of particle diameter <, 120 kg particle diameter 0.088-0 millimeter, 80 kilograms of particle diameter <
3n
4, 0.1 millimeter of 80 kilograms of particle diameter < Si, add in muller, mix 5 minutes, the dextrin that adds 16 kilograms, mixes 5 minutes, then adds 6% water, mix 20 minutes, the pug having mixed is pressed into adobe on 1000 tons of friction presses or other molding devices, through 200 ℃ of temperature dry 16 hours, dry after adobe at 1560 ℃ of temperature, through the nitrogenize of 100 hours, burn till that (air speed of nitrogen is than being 5.5h
-1), then in bituminizing liquid, flood 8 hours, finally at nitrogen, (air speed of nitrogen is than being 5.5h
-1) or bury 1500 ℃ of roastings in carbon, the time is 48 hours (while burying carbon, the weight ratio of fixed carbon and carbon metal compound composite material is 1.5: 1).
Its performance is: SiC account for gross weight 61.2%, C account for gross weight 12.5%, Si
3n
4account for gross weight 19.2%, void content 21.0%, volume density 2.58g/cm
3, compressive strength 185MPa, folding strength 25MPa, high temperature break resistant intensity (1400 * 0.5h ℃) 29MPa.
Embodiment 3:
The Si of 0.1 millimeter of the C of the SiC of 0.1 millimeter of the SiC of the SiC of 280 kilograms of particle diameter 3-1 millimeters, 56 kilograms of particle diameter 1-0.5 millimeters, 224 kilograms of particle diameter <, 120 kg particle diameter 0.088-0 millimeter, 64 kilograms of particle diameter <
3n
4, 0.1 millimeter of 56 kilograms of particle diameter < Si, add in muller, mix 5 minutes, the dextrin that adds 16 kilograms, mixes 5 minutes, then adds 6% water, mix 40 minutes, the pug having mixed is pressed into adobe on 1000 tons of friction presses or other molding devices, through 160 ℃ of temperature dry 84 hours, dry after adobe at 1450 ℃ of temperature, through the nitrogenize of 150 hours, burn till that (air speed of nitrogen is than being 2.9h
-1), then in bituminizing liquid, flood 48 hours, finally at nitrogen, (air speed of nitrogen is than being 2.9h
-1) or bury 600 ℃ of roastings in carbon, the time is 48 hours (while burying carbon, the weight ratio of fixed carbon and carbon metal compound composite material is 0.6: 1).
Its performance is: SiC account for gross weight 65.3%, C account for gross weight 12.1%, Si
3n
4account for gross weight 14.4%, void content 4.0%, volume density 2.85g/cm
3, compressive strength 230MPa, folding strength 50MPa, high temperature break resistant intensity (1400 * 0.5h ℃) 60MPa.
Embodiment 4:
The Si of 0.1 millimeter of the C of the SiC of 0.1 millimeter of the SiC of the SiC of 312 kilograms of particle diameter 3-1 millimeters, 63 kilograms of particle diameter 1-0.5 millimeters, 249 kilograms of particle diameter <, 80 kilograms of particle diameter 0.088-0 millimeters, 24 kilograms of particle diameter <
3n
4, 0.1 millimeter of 72 kilograms of particle diameter < Si, add in muller, mix 5 minutes, the dextrin that adds 16 kilograms, mixes 5 minutes, then adds 6% water, mix 25 minutes, the pug having mixed is pressed into adobe on 1000 tons of friction presses or other molding devices, through 180 ℃ of temperature dry 84 hours, dry after adobe at 1500 ℃ of temperature, through the nitrogenize of 150 hours, burn till that (air speed of nitrogen is than being 4.1h
-1), then in bituminizing liquid, flood 60 hours, finally at nitrogen, (air speed of nitrogen is than being 4.1h
-1) or bury 1000 ℃ of roastings in carbon, the time is 100 hours (while burying carbon, the weight ratio of fixed carbon and carbon metal compound composite material is 1.0: 1).
Its performance is: SiC account for gross weight 72.4%, C account for gross weight 8.1%, Si
3n
4account for gross weight 11.2%, void content 1.0%, volume density 3.00g/cm
3, compressive strength 350MPa, folding strength 58MPa, high temperature break resistant intensity (1400 * 0.5h ℃) 65MPa.
The matrix material of above-described embodiment is used on more than the 600 platform aluminium cells of 160KA, 180KA, 240KA, 300KA, and the ton aluminum direct current consumes does not reduce 200-1000 degree not etc. by domestic average consumption level 14000 degree, and on average reduction level is 600 degree.Further perfect along with electrolysis tech, the space that energy-saving effect is still improved.
Claims (3)
1. a method of preparing the carbon metal compound composite material that refining electrolytic bath uses, the main ingredient of described carbon metal compound composite material is SiC, C, Si
3n
4and Si, wherein SiC accounts for the 50-95% of gross weight, and C accounts for 1-33%, the Si of gross weight
3n
4account for the 1-35% of gross weight, Si accounts for the 0.1-30% of gross weight, and its key step is:
A) by SiC, C, Si
3n
4with Si in proportion weigh batching, aftershaping mixes;
B) matrix material of steps A gained is carried out to nitrogenize and burn till, temperature is 1380-1560 ℃, and the time is 100-200 hour;
C) matrix material of step B gained floods 8-60 hour in bituminizing liquid;
D) infused composite of step C gained is at nitrogen or 200-1500 ℃ of roasting in burying carbon, and the time is 48-200 hour.
2. the method for claim 1, wherein the nitrogen gas purity in step B and step D is 99.99%, and air speed is than being 1.8-5.5h
-1.
3. when the method for claim 1, wherein step D buries carbon, the weight ratio of fixed carbon and infused composite is 0.3-1.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010143076.1A CN102212844B (en) | 2010-04-07 | 2010-04-07 | Carbon metal compound composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010143076.1A CN102212844B (en) | 2010-04-07 | 2010-04-07 | Carbon metal compound composite material |
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| Publication Number | Publication Date |
|---|---|
| CN102212844A CN102212844A (en) | 2011-10-12 |
| CN102212844B true CN102212844B (en) | 2014-10-01 |
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ID=44744368
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010143076.1A Expired - Fee Related CN102212844B (en) | 2010-04-07 | 2010-04-07 | Carbon metal compound composite material |
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Families Citing this family (1)
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| CN104418593B (en) * | 2013-08-20 | 2016-09-07 | 沈阳铝镁科技有限公司 | A kind of high temperature resistant, resistance to erosion material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3562136A (en) * | 1967-03-24 | 1971-02-09 | Montedison Spa | Igneous-electrolysis multicell furnaces,for the protection of the inner layer in contact with molten salts |
| CN2062336U (en) * | 1989-10-13 | 1990-09-19 | 山东铝厂 | Aluminium electrolyser with combined sin and sic material as isde lining brick |
| CN1297066A (en) * | 1999-11-17 | 2001-05-30 | 钟群标 | Coating material for side of aluminium electrolyzer |
| CN101104565A (en) * | 2006-07-11 | 2008-01-16 | 揖斐电株式会社 | Composite ceramic powder, manufacturing method thereof and amoeboid refractory material |
| CN101591190A (en) * | 2009-06-29 | 2009-12-02 | 中国地质大学（北京） | A kind of aluminum electrolytic bath side wall New Si 3N 4-SiC-C refractory brick and preparation method thereof |
| CN101665365A (en) * | 2009-10-16 | 2010-03-10 | 攀钢冶金材料有限责任公司 | Refractory material of carbon protective sleeve and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56125276A (en) * | 1980-03-06 | 1981-10-01 | Kurosaki Refractories Co | Beta-sic-si3n4 composite specific heat-resistant ceramics and manufacture |
-
2010
- 2010-04-07 CN CN201010143076.1A patent/CN102212844B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3562136A (en) * | 1967-03-24 | 1971-02-09 | Montedison Spa | Igneous-electrolysis multicell furnaces,for the protection of the inner layer in contact with molten salts |
| CN2062336U (en) * | 1989-10-13 | 1990-09-19 | 山东铝厂 | Aluminium electrolyser with combined sin and sic material as isde lining brick |
| CN1297066A (en) * | 1999-11-17 | 2001-05-30 | 钟群标 | Coating material for side of aluminium electrolyzer |
| CN101104565A (en) * | 2006-07-11 | 2008-01-16 | 揖斐电株式会社 | Composite ceramic powder, manufacturing method thereof and amoeboid refractory material |
| CN101591190A (en) * | 2009-06-29 | 2009-12-02 | 中国地质大学（北京） | A kind of aluminum electrolytic bath side wall New Si 3N 4-SiC-C refractory brick and preparation method thereof |
| CN101665365A (en) * | 2009-10-16 | 2010-03-10 | 攀钢冶金材料有限责任公司 | Refractory material of carbon protective sleeve and preparation method thereof |
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| CN102212844A (en) | 2011-10-12 |
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