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 PDF

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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
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anode
modification
additive
electrolysis
prebaked
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CN1621565A (en
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肖劲
杨建红
李劫
叶绍龙
丁风其
刘红专
赖延清
刘业翔
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Central South University
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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

Be used for modification pre-baked carbon anode of electrolysis of aluminum and preparation method thereof
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
Figure C20031011058400041
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.
CNB200310110584XA 2003-11-28 2003-11-28 Modified prebaked carbon anode for aluminum electrolysis and preparation method thereof Expired - Fee Related CN1330793C (en)

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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

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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
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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
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