CN1330793C - Modified prebaked carbon anode for aluminum electrolysis and preparation method thereof - Google Patents
Modified prebaked carbon anode for aluminum electrolysis and preparation method thereof Download PDFInfo
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- CN1330793C CN1330793C CNB200310110584XA CN200310110584A CN1330793C CN 1330793 C CN1330793 C CN 1330793C CN B200310110584X A CNB200310110584X A CN B200310110584XA CN 200310110584 A CN200310110584 A CN 200310110584A CN 1330793 C CN1330793 C CN 1330793C
- Authority
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- Prior art keywords
- anode
- modification
- additive
- electrolysis
- prebaked
- Prior art date
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Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000654 additive Substances 0.000 claims abstract description 38
- 230000000996 additive effect Effects 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims description 36
- 230000004048 modification Effects 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 10
- 229910020068 MgAl Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 229910026161 MgAl2O4 Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052596 spinel Inorganic materials 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to aluminum electrolysis in nonferrous metallurgy, in particular to a carbon anode in prebaked aluminum electrolysis production, which is characterized in that: the additive content (weight percentage) in the prebaked carbon anode is as follows: 0.8-1.8% of AlF340-60 wt% of the whole additive component, MgAl2O430-40% (weight percentage); the invention improves the chemical and electrochemical properties of the anode, reduces the power consumption and carbon consumption of the anode in the working process, improves the aluminum electrolysis current efficiency, reduces the addition of aluminum fluoride in the electrolysis process, and stabilizes the electrolysis operation.
Description
Technical field
The present invention relates to the electrolysis of aluminum in the nonferrous metallurgy, the carbon anode during particularly prd-baked Al electrolysis is produced.
Background technology is described:
The performance of anode on the aluminium cell in electrolytic process directly has influence on energy consumption, charcoal consumption and the current efficiency of electrolysis of aluminum.The anode mix additive of prior art self-baking aluminium electrolytic bath research also has plenty of directly property-modifying additive is joined in self-roasting tank's ionogen; For prebaked cell for aluminum-reduction, just study around improving the aluminium electrolysis anode chemical property.
Summary of the invention:
The objective of the invention is: improve anodic chemistry and chemical property, make anode reach reduction power consumption and charcoal consumption in the course of the work, improve electrolysis of aluminum current efficiency, reduce aluminum fluoride addition in the electrolytic process, stablize electrolysis procedure.
Technical solution of the present invention is: with additive raw material, aluminium, magnesium, fluorine, oxygen compound on request weighing and with carbon anode aggregate uniform mixing, utilize the temperature of anode-baking to make anode in roasting process, finish the building-up reactions of additive, be prepared into the modification prebaked anode, it is characterized in that:
1. with the abundant mixing of additive raw material: 1～2 hour.
2. the additive raw material with mixing mixes with the carbon anode aggregate and preheating, the preheating of control continous way; Spiral outlet temperature: 140-160 ℃.
3. the compound of additive raw material and carbon anode aggregate is mixed and pinch, add simultaneously and dissolve pitch, control kneading machine (pot) heating agent inlet temperature: 200-230 ℃; Mixture temperature: 180-200 ℃; Mix and pinch the time: 2～3 hours.
4. will mix material and add compression moulding in the shaper, the modification prebaked anode is given birth to piece;
5. the modification prebaked anode is given birth to piece and place the roasting kiln roasting, finish the synthetic of additive in anode-baking, promptly be prepared into the modification prebaked anode, the sinter process parameter is as follows:
Maturing temperature: 1150-1250 ℃, roasting time (from going into stove): 450-480 hour to coming out of the stove.
Described modification prebaked anode contains Al, Mg, four kinds of masters of F, O contain element, and it at first is with AlF
3, MgO (perhaps Mg (OH)
2), Al (OH)
3(perhaps Al
2O
3) for additive adds in the carbon anode, serial chemical reaction takes place in these original components after the anode high-temperature roasting, finally they in anode with MgAl
2O
4And AlF
3Form have the main body component of Here it is modification prebaked anode.
Additive level in the pre-baked carbon anode of the present invention (weight percent) is: 0.8-1.8%, wherein AlF
3Account for the 40%-60% (weight percent) of whole binder component, MgAl
2O
4Account for 30-40% (weight percent);
If one ton of modification prebaked anode of preparation, its additive formula scope is as follows:
AlF
3Dosage: 4-12Kg/ ton anode;
MgO dosage: 0.34-0.84Kg/ ton anode, perhaps Mg (OH)
2Dosage: 0.493-1.218Kg/ ton;
Al (OH)
3Dosage: 1.4-3.25Kg/ ton anode, perhaps Al
2O
3Dosage: 1.831-4.25Kg/ ton.
The advantage and the positively effect of invention:
1. modification prebaked anode physical and chemical performance and chemical property are good, have significant volume increase and energy conservation and consumption reduction effects; The average charcoal consumption 11.6Kg/ ton aluminium that reduces on average reduces power consumption 106.1Kwh/ ton aluminium, and mean current efficient improves 0.72%.
Table 1 is the performance index that modification prebaked anode of the present invention uses, and itself and the anode (being called counter electrode) that uses are at present compared.
Table 1 modification prebaked anode and counter electrode chemical property detect table
In addition, the modification prebaked anode of industrial preparation has been carried out electrochemical property test, from modification prebaked anode and counter electrode superpotential η and the logarithmic graph of a relation of current density i as can be seen: when anodic current density is 1A/cm
2The time, the superpotential comparison of modification prebaked anode on average reduces about 52mV than anode, and this shows that the modification prebaked anode has the effect of good reduction anodic overvoltage.
2. additive is applied widely, is not subjected to grooved, groove condition and production-scale restriction, has popularizing application prospect widely.
On 160KA large-scale pre-baked aluminum electrolysis cell and 75KA small pre-calcining electrolytic cell, use the present invention, all obtained good implementation result, use the modification prebaked anode of such additive to compare with counter electrode, the average charcoal consumption 11.6Kg/ ton aluminium that reduces, the average power consumption 106.1Kwh/ ton aluminium that reduces, mean current efficient improves 0.72%.
3. the effect of anode modification is guaranteed because of the volatilization that has suppressed binder component in roasting.
In the additive building-up process, because Al (OH)
3, or Mg (OH)
2Fusing coat AlF
3And part MgO, or Mg (OH)
2) react the effect that all can reach solid fluorine, so reduce even avoided the volatilization of fluorine, guaranteed the anodic modified effect.
4. the additive cost is low, and raw material sources are extensive;
Used raw material A lF
3, MgO or Mg (OH)
2, Al (OH)
3Or Al
2O
3All are technical pure products, without any particular requirement.
Embodiment:
Embodiment 1: with the example that is prepared as of 160KA large-scale pre-baked aluminum electrolysis cell modification prebaked anode, concrete implementation step and processing parameter are as follows:
1. additive formulations calculates
The heavily about 780Kg/ piece of 160KA large-scale pre-baked aluminum electrolysis cell anode block (giving birth to piece), content of additive is calculated by 1.5% (weight percent) in the modification prebaked anode of preparation, presses AlF in the additive
3Account for 60%, MgAl
2O
4Account for 40% and calculate, then:
The every required additive preparation amount of anode is: 780 * 0.015=11.70Kg/ piece anode
Wherein: AlF
3Amount is: 11.7 * 0.6=7.02Kg; MgAl
2O
4Amount is: 11.7 * 0.4=4.68Kg.
By reaction equation
MgO+2Al(OH)
3＝MgAl
2O
4+3H
2O
Calculate, promptly get raw material MgO and Al (OH)
3Aequum separately:
Required MgO amount is: (4.68 * 40)/142=1.318Kg
Required Al (OH)
3Amount is: (4.68 * 156)/142=5.141Kg
By reaction equation
Mg(OH)
2+Al
2O
3＝MgAl
2O
4+H
2O
Calculate, promptly get raw material Mg (OH)
2And Al
2O
3Aequum separately:
Required Mg (OH)
2Amount is: (4.68 * 58)/142=1.912Kg
Required Al
2O
3Amount is: (4.68 * 102)/142=3.362Kg
Same method of calculation, if the additive level in the modification anode of preparation calculates by 0.8%, 1.2%, 1.8% (weight percent), then required material quantity is listed in table 2.
Different additive content desired raw material amount in the table 2 modification anode
| Additive is content (wt%) in anode | Desired additives amount (Kg/ piece anode) | AlF 3Amount (Kg) | MgAl 2O 4Amount (Kg) | ||
| Total amount | MgO/Mg(OH) 2 | Al(OH) 3/Al 2O 3 | |||
| 0.8 | 6.240 | 3.744 | 2.496 | 0.703/1.019 | 2.742/1.793 |
| 1.2 | 9.360 | 5.616 | 3.744 | 1.055/1.529 | 4.113/2.689 |
| 1.5 | 11.700 | 7.020 | 4.680 | 1.318/1.912 | 5.141/3.362 |
| 1.8 | 14.040 | 8.424 | 5.616 | 1.582/2.294 | 6.170/4.034 |
2. the preparation method of modification prebaked anode:
1. abundant mixing equipment used of additive raw material and processing parameter is as follows:
Equipment: dry type mixer; Mixing time: about 1～2 hour.
2. the additive raw material with mixing mixes with the carbon anode aggregate and preheating, and equipment used and processing parameter are as follows:
Equipment: continous way preheating spiral; Spiral outlet temperature: 140-160 ℃.
3. the compound of additive raw material and carbon anode aggregate is mixed and pinch, add simultaneously and dissolve pitch, equipment used and processing parameter are as follows:
Equipment: continous way kneading machine or intermittent type mix pinches pot; Kneading machine (pot) heating agent inlet temperature: 200-230 ℃;
Temperature: 180-200 ℃; Mix and pinch the time: 2 hours.
4. will mix material and add compression moulding in the shaper, and promptly get the modification prebaked anode and give birth to piece;
5. the modification prebaked anode is given birth to piece and place the roasting kiln roasting, finish the synthetic of additive in anode-baking, promptly be prepared into the modification prebaked anode, the sinter process parameter is as follows:
Maturing temperature: 1150-1250 ℃, roasting time (from going into stove): 450-480 hour to coming out of the stove.
3. modification prebaked anode index examination
Groove on the 700 polylith prebake modification prebaked anodes of preparation is carried out electrolytic trial, utilize the anode carbon consumption of anode scrap weighting method certification test groove and comparison groove, utilize catharometry and produce mode certification test groove that the aluminium weighting method combines and the current efficiency of comparison groove, utilize the average cell voltage value of mill count and current efficiency value to carry out energy consumption calculation.Industrial production statistics is the result show: use the modification prebaked anode of such additive to compare with counter electrode, on average reduce charcoal consumption 11.6Kg/ ton aluminium, on average reduce power consumption 106.1Kwh/ ton aluminium, mean current efficient improves 0.72%.
Claims (4)
1. be used for the preparation method of the modification pre-baked carbon anode of electrolysis of aluminum, it is characterized in that: AlF
3, MgO or Mg (OH)
2), Al
2O
3Or Al (OH)
3Additive raw material with carbon anode aggregate uniform mixing, utilizes the temperature of anode-baking to make anode finish the building-up reactions of additive in roasting process, is prepared into the modification prebaked anode.
2. the preparation method who is used for the modification pre-baked carbon anode of electrolysis of aluminum according to claim 1 is characterized in that:
1. with the abundant mixing of additive raw material: 1-2 hour;
2. the additive raw material with mixing mixes with the carbon anode aggregate and preheating, the preheating of control continous way; Spiral outlet temperature: 140-160 ℃;
3. the compound of additive raw material and carbon anode aggregate is mixed and pinch, add simultaneously and dissolve pitch, control kneading machine or mix and pinch pot heating agent inlet temperature: 200-230 ℃; Mixture temperature: 180-200 ℃; Mix and pinch the time: 2-3 hour;
4. will mix material and add compression moulding in the shaper, the modification prebaked anode is given birth to piece;
5. the modification prebaked anode is given birth to piece and place the roasting kiln roasting, finish the synthetic of additive in anode-baking, promptly be prepared into the modification prebaked anode, the sinter process parameter is as follows:
Maturing temperature: 1150-1250 ℃, from going into stove by the roasting time of coming out of the stove: 450-480 hour.
3. be used for the modification pre-baked carbon anode of electrolysis of aluminum, it is characterized in that: described weight of additive degree is: 0.8-1.8%, wherein AlF
3Account for the weight percent 40-60% of whole binder component, MgAl
2O
4Accounting for weight percent is 30%-40%.
4. the modification pre-baked carbon anode that is used for electrolysis of aluminum according to claim 3, it is characterized in that: described additive formula is as follows:
AlF
3Dosage: 4-12Kg/ ton anode;
MgO dosage: 0.34-0.84Kg/ ton anode, perhaps Mg (OH)
2Dosage: 0.493-1.218Kg/ ton;
Al (OH)
3Dosage amount: 1.4-3.25Kg/ ton anode, perhaps Al
2O
3Dosage: 1.831-4.25Kg/ ton.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200310110584XA CN1330793C (en) | 2003-11-28 | 2003-11-28 | Modified prebaked carbon anode for aluminum electrolysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200310110584XA CN1330793C (en) | 2003-11-28 | 2003-11-28 | Modified prebaked carbon anode for aluminum electrolysis and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1621565A CN1621565A (en) | 2005-06-01 |
| CN1330793C true CN1330793C (en) | 2007-08-08 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100582310C (en) * | 2007-06-07 | 2010-01-20 | 云南铝业股份有限公司 | Pre-baked anode for aluminum electrolysis and its preparation method |
| CN101353163B (en) * | 2007-07-26 | 2011-01-26 | 抚顺铝业有限公司 | Reclaiming powder adding method for pre-baked anode production |
| CN102188920A (en) * | 2010-03-09 | 2011-09-21 | 沈阳铝镁设计研究院有限公司 | Configuration structure for preheating screw machine and continuous kneading machine in production of carbon products |
| CN103266332B (en) * | 2013-05-24 | 2016-04-13 | 贵州师范大学 | A kind of modified prebaked carbon anode preparation method of Mg-containing additive |
| CN103255438A (en) * | 2013-05-24 | 2013-08-21 | 贵州师范大学 | Preparation method of modified pre-baked carbon anode containing titanium additive |
| CN105274571A (en) * | 2014-06-04 | 2016-01-27 | 贵阳铝镁设计研究院有限公司 | Method for covering aluminum electrolysis bath prebaked anode |
| CN108193232A (en) * | 2017-12-30 | 2018-06-22 | 贵阳铝镁设计研究院有限公司 | A kind of continuously pre-heating is interrupted kneading production technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039451A (en) * | 1989-07-29 | 1990-02-07 | 郑州轻金属研究所 | A kind of compound additive of anode for aluminium electrolysis |
| CN1043350A (en) * | 1989-11-24 | 1990-06-27 | 郑州轻金属研究所 | Aluminium cell flue dust reclaimed materials is used for a kind of method of electrolysis of aluminum |
| US5753382A (en) * | 1996-01-10 | 1998-05-19 | Moltech Invent S.A. | Carbon bodies resistant to deterioration by oxidizing gases |
-
2003
- 2003-11-28 CN CNB200310110584XA patent/CN1330793C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039451A (en) * | 1989-07-29 | 1990-02-07 | 郑州轻金属研究所 | A kind of compound additive of anode for aluminium electrolysis |
| CN1043350A (en) * | 1989-11-24 | 1990-06-27 | 郑州轻金属研究所 | Aluminium cell flue dust reclaimed materials is used for a kind of method of electrolysis of aluminum |
| US5753382A (en) * | 1996-01-10 | 1998-05-19 | Moltech Invent S.A. | Carbon bodies resistant to deterioration by oxidizing gases |
Non-Patent Citations (1)
| Title |
|---|
| 铝电解炭阳极添加氟化铝的形容与应用 刘凤琴 王平甫，有色金属(冶炼部分)，第5期 1997 * |
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