CN1039627A - The anode mix and the compound method thereof that are used for electrolysis of aluminum - Google Patents
The anode mix and the compound method thereof that are used for electrolysis of aluminum Download PDFInfo
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- CN1039627A CN1039627A CN 88104290 CN88104290A CN1039627A CN 1039627 A CN1039627 A CN 1039627A CN 88104290 CN88104290 CN 88104290 CN 88104290 A CN88104290 A CN 88104290A CN 1039627 A CN1039627 A CN 1039627A
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- Prior art keywords
- siccative
- pitch
- anode
- mix
- electrolysis
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 title description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003672 processing method Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 9
- 238000004898 kneading Methods 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 abstract description 17
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 abstract description 13
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 48
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000006253 pitch coke Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- -1 sodium aluminum fluoride Chemical compound 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The present invention is the new anode mix and the processing method thereof of used for aluminium electrolysis, it is characterized in that adding Quilonum Retard in used for aluminium electrolysis anode mix, and the amount that adds Quilonum Retard is the 0.09-0.9% (weight percentage) of siccative and pitch gross weight.This new anode mix can reduce overvoltage 110-250 millivolt, and by the condition of existing electrolysis of aluminum, aluminium per ton is saved consumption of direct current 369-837 degree.The blending process advantages of simple of new anode mix is suitable for industrial production, has replaced directly adding in the former oriented electrolyzer operation of Quilonum Retard.Reduced the loss of flying upward of Quilonum Retard, made lithium fluoride stable content in the ionogen.Improved the current efficiency of electrolysis of aluminum.
Description
The invention belongs to used for aluminium electrolysis anode mix and compound method thereof, in the anode mix of used for aluminium electrolysis, mix Quilonum Retard (Li
2CO
3) after, can reduce the anode overvoltage, thereby reach the purpose of saves energy.
The method of electrolytic aluminum in the Cryolite-Alumina system, since the Hall-Heroult patent of invention, existing centenary history, aluminium electrolytic industry is still continued to use this method now, this method energy consumption is big, its electric energy efficiency has only 40%, under current energy starved situation, and the energy-conservation outstanding problem that becomes aluminium industry how.
The production of laboratory and factory all proves, in industrial current density range, the counter-electromotive force that the two poles of the earth produce is the 1.6-1.7 volt, more much bigger than theoretical decomposition voltage value (1.08-1.19 volt), the difference of these two is negative electrode overvoltage and anode overvoltage sum, and the negative electrode overvoltage is very little, be generally the 40-80 millivolt, the anode overvoltage then accounts for 80-90%, is about the 0.4-0.6 volt, and so high anode overvoltage has caused very big waste of energy.But for a long time, people think that the anode overvoltage in the electrolysis of aluminum is difficult to reduce.In recent years, the work of domestic this respect has had certain progress, Xiao of Zhongnan Polytechnic Univ hamming, Liu Yexiang deliver the paper (1986 that is entitled as " electro catalytic activity of different doping carbon anodes research during electrolysis of aluminum " in the academic annual meeting of national light metal in 8 or six years, 1), this paper is said, as anode material, it is mixed Li with the spectroscopically pure graphite rod with physics or chemical process
2CO
3, being used for electrolysis of aluminum then, discovery can reduce about 0.2 volt of anode overvoltage, but this paper is not to doping process, Li
2CO
3Content and effect thereof are made detailed report.
Existing anode mix production technique generally is such, under 1150-1350 ℃ temperature, with siccative calcination in rotary kiln, again through the jaw crusher fragmentation, the granularity requirements of broken back siccative: φ 2-4: 21-26%, φ 1-2: 10-16%, φ 0-1 do not require, φ (0.15)-0.075: 45-51%; Qualified siccative is prepared burden with pitch again, requires siccative: pitch=(68-72): (28-32); The bituminous temperature is greater than 140 ℃; Pinch mixing to pinch to mix in the pot then, mix the temperature requirement pinched between 130-170 ℃, mix and pinch, pour institute at last into and require in the shapes of containers water cooling moulding until evenly.
The objective of the invention is to work out a kind of new anode mix, find out Li in this new anode mix
2CO
3Suitable content range, make it have the effect that reduces the anode overvoltage significantly, thereby reduce the power consumption of electrolysis of aluminum significantly.
Another object of the present invention is to find out the processing method that a kind of anode mix of advantages of simple is mixed Quilonum Retard, to adapt to big industrial production.
A further object of the present invention is to find out a kind of new Li that adds in aluminium cell
2CO
3Method, to replace directly in electrolyzer, adding originally Li
2CO
3Method, thereby reduce Li
2CO
3Mechanical loss, reduce labour intensity, overcome shortcomings such as lithium fluoride in the ionogen (LiF) content instability.
The present invention is a kind of new anode mix, and it is to account for by account for 68-72% and pitch through calcination, the qualified siccative in broken back that 28-32% and Quilonum Retard are mixed to be pinched formulatedly, and it adds Li
2CO
3Amount be that the above-mentioned percentage ratio of 0.09-0.9%(of siccative and pitch weight sum is weight percentage, as follows).This new anode mix can reduce anode overvoltage 110-250 millivolt.
In order to prepare a kind of new anode mix of the present invention, its processing method is with siccative calcination under 1150-1350 ℃ temperature, siccative after fragmentation is qualified accounts for 68-72% and accounts for 28-32% and Quilonum Retard greater than 140 ℃ pitch and mix and pinch to evenly, mixing the temperature pinch is 130-170 ℃, mixes wherein a kind of mode of pinching in preceding, siccative and the pitch kneading process at siccative and pitch and adds Li
2CO
3, Li
2CO
3Add-on be the 0.09-0.9% of siccative and pitch weight sum.
In order to reduce the anode overvoltage biglyyer, reduce the power consumption of electrolysis of aluminum, add Li in the new anode mix
2CO
3Amount be that the 0.20-0.45% of siccative and pitch weight sum is for well.The Li that in anode mix, contains the 0.20-0.45% of promising siccative and pitch weight sum
2CO
3, can reduce anode overvoltage 170-250 millivolt; And Li in the anode mix
2CO
3Content less than siccative and pitch weight sum 0.2% or greater than accounting for 0.45% of siccative and pitch weight sum, it is relatively poor to reduce anode overvoltage effect.Li in the anode mix
2CO
3Content should be less than 0.09% of siccative and pitch weight sum, should be greater than 0.9% of siccative and pitch weight sum yet, this is because electrolysis of aluminum is at sodium aluminum fluoride (Na
3ALF
6) an aluminum oxide (Al
2O
3) carry out in the molten salt system, this individual system is issued to balance in used electrolysis production condition, and its physicochemical property (as the primary crystal temperature, than resistance, viscosity etc.) also reach stable, and all advantages of the present invention are to be based upon not destroy Na
3AlF
6-Al
2O
3On the system equilibrated basis.If Li in the anode mix
2CO
3Add-on reduced the poor effect of anode overvoltage greater than 0.9% o'clock of siccative and pitch weight sum, and that main is high-load Li in the anode mix
2CO
3Along with anodic consumption falls into electrolyzer, cause a large amount of accumulation, so that destroy Na
3AlF
6-Al
2O
3The balance of system; If add Li in the anode mix
2CO
3Amount less than siccative and pitch weight sum 0.09% o'clock, the effect that reduces the anode overvoltage is not good yet, can not keep Na separately in addition
3AlF
6-Al
2O
3The basic content of lithium fluoride in the system.
The said siccative of the present invention is wherein a kind of of refinery coke, pitch coke, coking Jiao, or the mixture of two kinds, three kinds suitable proportions, with pure refinery coke, pitch coke for well.Siccative granularity requirements after the jaw crusher fragmentation is same as the prior art, and is in common knowledge for those skilled in the art, is specially: φ 2-4: 21-26%, and φ 1-2: 10-16%, φ 0-1 does not require, φ (0.15)-0.075: 45-51%.Siccative is calcination in rotary kiln, and the temperature of calcination is between 1150 °-1350 ℃, if be lower than 1150 ℃, the physical and chemical performance of siccative after the calcination (as ash, fugitive constituent, proportion etc.) does not reach requirement; If greater than 1350 ℃, then cause energy dissipation, also make rotary kiln be easy to breakage.The bituminous temperature must not be lower than 140 ℃ between 140 °-160 ℃, otherwise pitch is unfavorable for mixed pinching too firmly; If greater than 160 ℃, then waste energy, kneading temperature remains on 130 °-170 ℃ for well, to be suitable for the keeping bituminous temperature, to help mixing and pinches.Mix the time pinch with 40-60 minute for good, keeps enough mixed pinching the time, with guarantee to mix pinch evenly, but mixed to pinch the time oversize, then is the waste of manpower and materials.
In anode mix, mix Li simultaneously into the 0.09-0.9% of siccative and pitch weight sum
2CO
3With the magnesium fluoride (MgF that is the 0.1-0.5% of siccative and pitch weight sum
2), also can reduce about 100 millivolts of anode overvoltages, its effect is mixed the Li into the 0.09-0.9% of siccative and pitch weight sum more separately
2CO
3Difference.
A kind of new anode mix of the present invention is mixed Li
2CO
3Mode have two kinds, first kind is the Li that once adds aequum before pinching mixing
2CO
3; Second method is the Li with aequum
2CO
3In kneading process, add several times.Li in the anode mix of second method
2CO
3Distribution even a little than the anode mix of first method, but Li
2CO
3Mechanical loss is bigger in the interpolation process.
Replace Li with lithium salts such as lithium fluoride (LiF), lithium chlorides
2CO
3Join in the anode mix, can obtain and add Li
2CO
3Similar effects, but the price of lithium salts such as lithium fluoride, lithium chloride is than Li
2CO
3So costliness is to add Li
2CO
3Best.
When a kind of new anode mix of the present invention is used for the self-roasting tank, puts into and consume shallow anode case, rely on the automatic roasting of temperature of electrolysis self to become anode; When being used to give the roasting groove, roasting in advance becomes anode in the container of requirement specification, is used further on the electrolyzer, and its technological process is that those skilled in the art are in common knowledge.
Advantage of the present invention is: the first, and a kind of new anode mix of the present invention can reduce anode overvoltage 110-250 millivolt.Under existing working condition, current efficiency is 89%, and then the consumption of direct current of aluminium per ton reduces the 368-837 degree.
The second, a kind of new anode mix compounding process advantages of simple of the present invention is suitable for big industrial production.Anode mix is mixed Li
2CO
3Process need not to increase equipment, do not increase the cost of Aluminium Electrolysis, because the original Li that just needs to consume same amount yet
2CO
3
The 3rd, a kind of new anode mix of the present invention is used for aluminium electrolysis anode, also is along with anode consumption Li wherein
2CO
3Evenly fall into electrolyzer, in electrolyzer, directly add Li originally thereby replaced
2CO
3Link, reduced labour intensity, reduced Li
2CO
3Fly upward loss, and overcome the original Li that directly adds
2CO
3Inhomogeneous and cause the unsettled shortcoming of lithium fluoride content in the ionogen.
The 4th, a kind of new anode mix of the present invention also can reduce the consumption of aluminium electrolysis anode, has promptly reduced the carbon consumption.Because reducing the anode overvoltage is exactly the speed of response of having accelerated carbon and oxygen, promptly the speed of response of the fixed carbon in siccative and the pitch and oxygen is tending towards synchronously in the anode mix, has then overcome preferentially consumption and cause the phenomenon of peeling off of siccative of fixed carbon in the pitch.
The 5th, a kind of new anode mix of the present invention can improve the current efficiency of electrolysis of aluminum.Because Li
2CO
3Can quicken the speed of response of oxygen and carbon, reality has just reduced the chance that aluminium contacts with oxygen on anode, has promptly reduced the secondary reaction loss of aluminium.
Following indefiniteness embodiment more specifically describes the present invention, and protection scope of the present invention is not subjected to the qualification of these embodiment.
Embodiment one
With pitch coke calcination under 1250 ℃ temperature in rotary kiln, it is qualified to be crushed to granularity through jaw crusher again; Pitch is heated to 145 ℃ again; In following ratio batching, pitch coke: pitch=70: 30, and mix pitch coke and pitch weight and 0.40% Li
2CO
3, placing to mix and pinch pot and mix and pinch, 140 ℃ of kneading temperatures, are poured water cooling moulding in the container of terrace with edge shape of 500 kg capacity at last at 50 minutes time.Before the moulding, pinch five different sites sampling analysis Li in the pot mixing
2CO
3Content, the result is 0.44%, 0.37%, 0.40%, 0.38%, 0.44%, shows Li
2CO
3In anode mix, be evenly distributed, and mechanical loss is very little in the interpolation process.In addition, again this new anode mix is done physical and chemical performance analysis, and make comparisons with original anode mix, it the results are shown in Table one.
As can be seen from Table I, the physicochemical property of a kind of new anode mix of the present invention and original anode mix are basic identical, illustrate that also antianode mixes an amount of Quilonum Retard its physicochemical property are not had detrimentally affect.
Above-mentioned anode mix is used for the self-baking aluminium electrolytic bath of existing production, and main production specifications are as follows:
Anodic current density: 0.95A/cm
2,
Operating voltage: 4.200V,
Alumina concentration (weight): 3.17%
Ionogen height: 16-18cm,
Aluminium liquid height: 28-32cm.
Measure its anode overvoltage with L type graphite reference electrode, compare with the anode overvoltage of original anode mix, the result shows, the anode overvoltage of this new anode mix reduces 250mv than the anode overvoltage of original anode mix, recording current efficiency simultaneously is 89%, and then the unit dc consumption of Jie Yueing is by formula:
△P＝2980 (△V)/(CE)
(CE is a current efficiency for the unit dc consumption of △ P for reducing, the magnitude of voltage of △ V for reducing)
Calculate △ P=837 degree/ton aluminium.
Embodiment two
Compound method, physico-chemical property and electrolysis production major technique condition and embodiment one are basic identical, only Li
2CO
3Incorporation be pitch coke and pitch weight and 0.1%.When anodic current density is 0.85A/cm
2The time, reducing the anode overvoltage is 180mv; When anodic current density is 1.00A/cm
2The time, reducing the anode overvoltage is 174mv.
Embodiment three
Compound method, physico-chemical property and electrolysis production major technique condition and embodiment one are basic identical, only Li
2CO
3Incorporation be pitch coke and pitch weight and 0.2%.When anodic current density is 0.85A/cm
2The time, the anode overvoltage of reduction is 181mv; When anodic current density is 1.00A/cm
2The time, the anode overvoltage of reduction is 175mv.
Embodiment four
Compound method, physico-chemical property and electrolysis production major technique condition and embodiment one are basic identical, only Li
2CO
3Incorporation be pitch coke and pitch weight and 0.6%.When anodic current density is 0.85A/cm
2The time, reducing the anode overvoltage is 176mv; When anodic current density is 100A/cm
2The time, the anode overvoltage of reduction is 157mv.
Embodiment five
Compound method, physico-chemical property and electrolysis production major technique condition and embodiment one are basic identical, only Li
2CO
3Incorporation be pitch coke and pitch weight and 0.8%.When anodic current density is 0.85A/cm
2The time, reduce anode overvoltage 110mv; When anodic current density is 1.00A/cm
2The time, the anode overvoltage of reduction is 136mv.
Claims (3)
1, a kind of anode mix that is used for electrolysis of aluminum newly, it is to account for 28-32% and Quilonum Retard (Li by account for 68-72% (weight percentage, down together) through calcination, the qualified siccative in broken back with pitch
2CO
3) formulated, the add-on that it is characterized in that Quilonum Retard is the 0.09-0.9% of siccative and pitch weight sum.
2, the processing method for a kind of new anode mix of preparing claim 1 is, with siccative calcination under 1150-1350 ℃ temperature, account for the 68-72%(weight percentage through being crushed to the siccative of granularity after qualified, down with) with account for 28-32% and Quilonum Retard greater than 140 ℃ pitch and mix and pinch to evenly, mixing the temperature of pinching is 130-170 ℃, it is characterized in that mixing a kind of mode wherein of pinching in preceding, siccative and the pitch kneading process at siccative and pitch adds Quilonum Retard, the add-on of Quilonum Retard is the 0.09-0.9% of siccative and pitch weight sum.
3, according to the processing method of a kind of new anode mix of claim 2, the Quilonum Retard amount of its adding is the 0.20-0.45% of siccative and pitch weight sum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88104290 CN1011314B (en) | 1988-07-21 | 1988-07-21 | Anode pasty for aluminium electrolysis and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88104290 CN1011314B (en) | 1988-07-21 | 1988-07-21 | Anode pasty for aluminium electrolysis and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1039627A true CN1039627A (en) | 1990-02-14 |
| CN1011314B CN1011314B (en) | 1991-01-23 |
Family
ID=4832958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88104290 Expired CN1011314B (en) | 1988-07-21 | 1988-07-21 | Anode pasty for aluminium electrolysis and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011314B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112014265A (en) * | 2020-08-05 | 2020-12-01 | 中国铝业股份有限公司 | Continuous anode aluminum cell anode paste performance evaluation device and evaluation method |
-
1988
- 1988-07-21 CN CN 88104290 patent/CN1011314B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112014265A (en) * | 2020-08-05 | 2020-12-01 | 中国铝业股份有限公司 | Continuous anode aluminum cell anode paste performance evaluation device and evaluation method |
| CN112014265B (en) * | 2020-08-05 | 2024-01-23 | 中国铝业股份有限公司 | Device and method for evaluating anode paste performance of continuous anode aluminum electrolysis cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1011314B (en) | 1991-01-23 |
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