CN103741167A - Method for improving oxidization resistance of carbon anode for electrolyzing aluminum - Google Patents
Method for improving oxidization resistance of carbon anode for electrolyzing aluminum Download PDFInfo
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- CN103741167A CN103741167A CN201310724749.6A CN201310724749A CN103741167A CN 103741167 A CN103741167 A CN 103741167A CN 201310724749 A CN201310724749 A CN 201310724749A CN 103741167 A CN103741167 A CN 103741167A
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Abstract
The invention discloses a method for improving the oxidization resistance of a carbon anode for electrolyzing aluminum and belongs to methods for manufacturing the carbon anode for the aluminum. The method comprises the following steps: soaking a molded carbon anode green body or a baked carbon anode into a solution of H3BO3 or a compound containing B so that the H3BO3 or the compound containing the B reaches the surface of the carbon anode for electrolyzing the aluminum and an opening air hole on the surface and enable the solution with the certain concentration of the H3BO3 or the compound containing the B to enter a micro-pore with a certain depth on the surface layer of the carbon anode, so as to realize covering and filling effects; sealing an active part on the surface of carbon by glass-shape-like B2O3 generated under a following baking or electrolyzing temperature so as to stop a high-temperature diffusion reaction of air and CO2, reduce the consumption of high-quality carbon resources and carbon emission, relieve the labor intensity of electrolytic cell operators and reduce the production cost of virgin aluminum. According to the method, a formed oxidization-resisting protective film is very dense and the bonding strength with the carbon anode is very high; the implementation is very simple and a current carbon anode production process basically does not need to be changed.
Description
Technical field
The present invention relates to a kind of method of manufacturing aluminum carbon anode, particularly a kind of method that improves electrolytic aluminum carbon anodic anti-oxidation.
Technical background
The production of fine aluminium at present mainly adopts sodium aluminum fluoride-alumina molten salt electrolysis method of Hall-Heroult, and its anode material is a kind of consumptive carbon product, is " heart " of electrolytic aluminum.Carbon anode consumption is one of prime cost of Aluminum Electrolysis Production, accounts for 15% left and right of total cost.In Aluminum Electrolysis Production process, carbon anode consumption comprises electrochemistry consumption, chemical depletion and machinery consumption etc.Wherein carbon anode and CO
2the chemical depletion that the oxidizing reaction at high temperature occurring with air causes is the main reason of anode luxus consumption, accounts for 7%～20% of whole charcoal consumption.And the too fast consumption of anode, can cause the replacement frequency of anode to increase, this not only can increase workman's labour intensity, and can cause the energy-efficient Technology of modern times take low anode effect as principal character to be difficult to smooth enforcement, the Efficiency Decreasing of electrolyzer.If can slow down the high temperature oxidation speed of carbon anode, will be conducive to reduce production costs, reduce labor strength, reduce carbonic acid gas row.
From current result of study, the method that improves carbon anode oxidation-resistance both at home and abroad has following a few class: (1) improves the oxidation-resistance of carbon anode by controlling the method for Petroleum Coke, in major control refinery coke, oxidizing reaction is had the content of the impurity element of katalysis.(2) coal-tar pitch is carried out to study on the modification, by adjusting softening temperature, toluene insolubles content and three of the β resin contents of coal-tar pitch, improve the coking character of coal-tar pitch, improve coal-tar pitch Jiao's oxidation-resistance.(3) carbon anode is carried out to modification, adopt additive to reduce the oxidation activity of carbon anode.(4) method of top coat, comprises and adopts melting or spraying aluminium film in methods such as carbon anode surface-coated one deck compound anti-oxidation films, to stop air to contact with carbon anode as protective membrane, employing.(5) conventionally adopt in industrial production at present technique at anode top capping oxidation aluminum feedstock protective layer to reduce the oxidation of anode.But alumina raw material protective layer is loose, hole is large, inhomogeneous, adds anode side and is still exposed to the CO that electrolytic reaction produces
2in, the effect that reduces the anode luxus consumption causing because of anodic oxidation is limited.And the method for coating is also difficult in the industrial application of succeeding, this is mainly because coating can be dissolved in cryolite fused salt, and separates out the impurity that can pollute Aluminum.Secondly, the cohesiveness between coating and Carbon Materials is poor.The most important thing is air and CO
2the degree of depth that conventionally can diffuse to carbon anode top layer 5cm～10cm is carried out oxidizing reaction, and refinery coke aggregate self has a kind of mushy structure, the hole that shallow layer only can confining surface, and very micro-to the interception of this diffusion reaction.Therefore, better terms of settlement is exactly to make this protective layer can form fine and close protective membrane under high-temperature condition, isolated air and CO
2with contacting of carbon, reduce oxidizing reaction.
Summary of the invention
Technical problem: the object of the invention is to overcome the weak point existing in prior art, a kind of coating of the internal surface that can cover carbon anode surface and surface opening micropore is provided, make carbon anode at high temperature there is opposing air and CO
2the ability of diffusion and reaction, reduces the consumption of carbon anode, saves production cost, improves the method for electrolytic aluminum carbon anodic anti-oxidation.
Technical scheme: the present invention improves the method for electrolytic aluminum carbon anodic anti-oxidation, immerses H immediately by the carbon anode green compact after moulding
3bO
3or cooling containing carrying out in the compound solution of B, or the carbon anode after roasting is immersed to H
3bO
3or containing in the compound solution of B, solution can be arrived in electrolytic aluminum carbon anode surface and surperficial open pore thereof, to carbon anode green compact carrying out forming protective film in roasting process; Or at electrolysis temperature, be to form protective film at 950 ℃～970 ℃ to carbon anode; The enforcement of carbon anode anti-oxidation protection film comprises configuration H
3bO
3or contain compound solution, dipping, the roasting of B or be dried, concrete steps are as follows:
(1) preparation H
3bO
3or containing the compound solution of B: by H
3bO
3or containing the compound dissolution of B in water, strength of solution is 1～20wt.%, solution temperature is 20～70 ℃, is stirred, and makes H
3bO
3or all dissolve containing the compound of B;
(2) dipping: the carbon anode green compact after extrusion molding or vibratory compaction are immersed to the H preparing immediately
3bO
3or cooling containing carrying out in the compound solution of B, or the carbon anode after roasting is immersed to H
3bO
3or containing in the compound solution of B, soak taking-up in 10-60 minute, solution can be arrived in the surperficial and surperficial open pore of electrolytic aluminum carbon anode;
(3) roasting or dry: carry out roasting according to conventional roasting process after the seasoning of carbon anode green compact; Carbon anode after roasting adopts the mode of seasoning or heating, drying.
Beneficial effect, owing to having adopted such scheme, through roasting (for carbon anode green compact) or the reaction of (for the carbon anode after roasting) under electrolysis temperature, in carbon anode surface and surface opening pore, form the compound of one deck containing B, this stratification compound at high temperature forms similar glassy mass, sealed the reactive site on carbon surface, this has just intercepted carbon anode and air and CO
2contact reacts and the oxidizing reaction of being brought by their diffusion, reduce high-quality carbon element resource consumption and reduce carbon emission, alleviate the labour intensity of electrolytic cell operation work, reduce the production cost of primary aluminum.Also aluminum oxide tectum on the present aluminum electrolytic tank carbon anode of attenuate to a certain extent of this anti oxidation layer, meets the requirement of electrolyzer top heat dissipation, optimizes electrolyzer thermal equilibrium, increases cell life.
Advantage: make H
3bO
3or enter in the degree of depth micropore on carbon anode top layer containing the compound solution of B, play the effect that covers and fill, under roasting process (for carbon anode green compact) subsequently or electrolysis temperature, (for the carbon anode after roasting) generates similar glass B
2o
3seal the reactive site on carbon surface, stoped air and CO
2high temperature diffusion reaction, reduced high-quality carbon element resource consumption and reduced carbon emission, alleviated the labour intensity of electrolytic cell operation work, reduced the production cost of primary aluminum.The anti-oxidation protection film that present method forms is very fine and close, and carbon anode bonding strength is high, and implements simply, substantially not need to change existing carbon anode production art.
Embodiment:
The present invention improves the method for electrolytic aluminum carbon anodic anti-oxidation, and the carbon anode green compact after moulding are immersed to H immediately
3bO
3or cooling containing carrying out in the compound solution of B, or the carbon anode after roasting is immersed to H
3bO
3or containing in the compound solution of B, solution can being arrived in electrolytic aluminum carbon anode surface and surperficial open pore thereof, carbon anode green compact are carrying out forming protective film in roasting process or carbon anode is to form protective film at 950 ℃～970 ℃ at electrolysis temperature; The embodiment of carbon anode anti-oxidation protection film comprises configuration H
3bO
3or contain compound solution, dipping, the roasting (for carbon anode green compact) of B or be dried (for the carbon anode after roasting), concrete steps are as follows:
(1) preparation H
3bO
3or containing the compound solution of B: by H
3bO
3or containing the compound dissolution of B in water, strength of solution is 1～20wt.%, solution temperature is 20～70 ℃, is stirred, and makes H
3bO
3or all dissolve containing the compound of B;
(2) dipping: the carbon anode green compact after extrusion molding or vibratory compaction are immersed to the H preparing immediately
3bO
3or cooling containing carrying out in the compound solution of B, or the carbon anode after roasting is immersed to H
3bO
3or containing in the compound solution of B, soak taking-up in 10-60 minute, solution can be arrived in the surperficial and surperficial open pore of electrolytic aluminum carbon anode;
(3) roasting or dry: carry out roasting according to conventional roasting process after the seasoning of carbon anode green compact; Carbon anode after roasting adopts the mode of seasoning or heating, drying.
Embodiment 1: it is that 15%wt.%, temperature are the H of 60 ℃ that the carbon anode green compact of vibratory compaction are immersed to concentration immediately
3bO
3in solution, carry out coolingly, soak 30 minutes, pull out after seasoning, the carbon anode roasting heating curve of peace more solito carries out after roasting standby, carries out forming protective film in roasting process.Adopt iso-thermal TGA method to measure atmospheric oxygen voltinism and the CO of carbon anode
2reactivity, shows with the simultaneous test of impregnated carbon anode not, 550 ℃ of atmospheric oxygen voltinisms of carbon anode have reduced by 70%, 970 ℃ of CO of carbon anode
2reactivity has reduced by 15%.
Embodiment 2: it is that 10wt.%, temperature are the H of 50 ℃ that the carbon anode green compact of vibratory compaction are immersed to concentration immediately
3bO
3in solution, carry out coolingly, soak 25 minutes, pull out after seasoning, the carbon anode roasting heating curve of peace more solito carries out using after roasting.Adopt iso-thermal TGA method to measure atmospheric oxygen voltinism and the CO of carbon anode
2reactivity, shows with the simultaneous test of impregnated carbon anode not, reduces by 550 ℃ of atmospheric oxygen voltinisms 67% of carbon anode, reduces by 970 ℃ of CO of carbon anode
2reactive 13%.
Embodiment 3: it is that 2wt.%, temperature are the H of 35 ℃ that the carbon anode green compact of vibratory compaction are immersed to concentration immediately
3bO
3in solution, carry out coolingly, soak 30 minutes, pull out after seasoning, the carbon anode roasting heating curve of peace more solito carries out using after roasting.Adopt iso-thermal TGA method to measure atmospheric oxygen voltinism and the CO of carbon anode
2reactivity, shows with the simultaneous test of impregnated carbon anode not, reduces by 550 ℃ of atmospheric oxygen voltinisms 15% of carbon anode, reduces by 970 ℃ of CO of carbon anode
2reactive 10%.
Embodiment 4: it is that 5wt.%, temperature are the H of 45 ℃ that the carbon anode after roasting is immersed to concentration
3bO
3in solution, soak 60 minutes, use after pulling seasoning out.Adopt iso-thermal TGA method to measure atmospheric oxygen voltinism and the CO of carbon anode
2reactivity, shows with the simultaneous test of impregnated carbon anode not, reduces by 550 ℃ of atmospheric oxygen voltinisms 65% of carbon anode, reduces by 970 ℃ of CO of carbon anode
2reactive 20%.
Embodiment 5: it is that 10wt.%, temperature are the H of 50 ℃ that the carbon anode after roasting is immersed to concentration
3bO
3in solution, soak 40 minutes, pull out to adopt after hot-air seasoning and use.Adopt iso-thermal TGA method to measure atmospheric oxygen voltinism and the CO of carbon anode
2reactivity, shows with the simultaneous test of impregnated carbon anode not, reduces by 550 ℃ of atmospheric oxygen voltinisms 53% of carbon anode, reduces by 970 ℃ of CO of carbon anode
2reactive 16%.
Claims (1)
1. a method that improves electrolytic aluminum carbon anodic anti-oxidation, is characterized in that: the carbon anode green compact after moulding are immersed to H immediately
3bO
3or cooling containing carrying out in the compound solution of B, or the carbon anode after roasting is immersed to H
3bO
3or containing in the compound solution of B, solution can be arrived in electrolytic aluminum carbon anode surface and surperficial open pore thereof, to carbon anode green compact carrying out forming protective film in roasting process; Or at electrolysis temperature, be to form protective film at 950 ℃～970 ℃ to carbon anode; The enforcement of carbon anode anti-oxidation protection film comprises configuration H
3bO
3or contain compound solution, dipping, the roasting of B or be dried, concrete steps are as follows:
(1) preparation H
3bO
3or containing the compound solution of B: by H
3bO
3or containing the compound dissolution of B in water, strength of solution is 1～20wt.%, solution temperature is 20～70 ℃, is stirred, and makes H
3bO
3or all dissolve containing the compound of B;
(2) dipping: the carbon anode green compact after extrusion molding or vibratory compaction are immersed to the H preparing immediately
3bO
3or cooling containing carrying out in the compound solution of B, or the carbon anode after roasting is immersed to H
3bO
3or containing in the compound solution of B, soak taking-up in 10-60 minute, solution can be arrived in the surperficial and surperficial open pore of electrolytic aluminum carbon anode;
(3) roasting or dry: carry out roasting according to conventional roasting process after the seasoning of carbon anode green compact; Carbon anode after roasting adopts the mode of seasoning or heating, drying.
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|---|---|---|---|
| CN201310724749.6A CN103741167A (en) | 2013-12-25 | 2013-12-25 | Method for improving oxidization resistance of carbon anode for electrolyzing aluminum |
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|---|---|---|---|
| CN201310724749.6A CN103741167A (en) | 2013-12-25 | 2013-12-25 | Method for improving oxidization resistance of carbon anode for electrolyzing aluminum |
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|---|---|
| CN103741167A true CN103741167A (en) | 2014-04-23 |
Family
ID=50498230
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Cited By (6)
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|---|---|---|---|---|
| CN104120454A (en) * | 2014-07-01 | 2014-10-29 | 湖南创元铝业有限公司 | Prebaked anode oxidation-resistant ceramic-based coating and coating method thereof |
| CN113388864A (en) * | 2021-06-23 | 2021-09-14 | 中国铝业股份有限公司 | Carbon anode for low-carbon-slag aluminum electrolysis and preparation method thereof |
| CN114016087A (en) * | 2021-10-28 | 2022-02-08 | 湖南国发控股有限公司 | Formula of efficient silicon-boron system impregnant and preparation and application processes thereof |
| CN114100895A (en) * | 2021-10-28 | 2022-03-01 | 湖南国发控股有限公司 | Carbon electrode cooling and anti-oxidation treatment integrated control system and method |
| CN114315356A (en) * | 2022-01-21 | 2022-04-12 | 东北大学 | Aluminum electrolysis carbon anode oxidation resistant coating and preparation method thereof |
| CN116813386A (en) * | 2023-06-30 | 2023-09-29 | 广西大学 | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof |
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| CN104120454A (en) * | 2014-07-01 | 2014-10-29 | 湖南创元铝业有限公司 | Prebaked anode oxidation-resistant ceramic-based coating and coating method thereof |
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| CN113388864A (en) * | 2021-06-23 | 2021-09-14 | 中国铝业股份有限公司 | Carbon anode for low-carbon-slag aluminum electrolysis and preparation method thereof |
| CN114016087A (en) * | 2021-10-28 | 2022-02-08 | 湖南国发控股有限公司 | Formula of efficient silicon-boron system impregnant and preparation and application processes thereof |
| CN114100895A (en) * | 2021-10-28 | 2022-03-01 | 湖南国发控股有限公司 | Carbon electrode cooling and anti-oxidation treatment integrated control system and method |
| CN114315356A (en) * | 2022-01-21 | 2022-04-12 | 东北大学 | Aluminum electrolysis carbon anode oxidation resistant coating and preparation method thereof |
| CN116813386A (en) * | 2023-06-30 | 2023-09-29 | 广西大学 | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof |
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Application publication date: 20140423 |