CN100507091C - Metal-base composite material inert anode for aluminium electrolysis and preparation method thereof - Google Patents
Metal-base composite material inert anode for aluminium electrolysis and preparation method thereof Download PDFInfo
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- CN100507091C CN100507091C CNB2005100476697A CN200510047669A CN100507091C CN 100507091 C CN100507091 C CN 100507091C CN B2005100476697 A CNB2005100476697 A CN B2005100476697A CN 200510047669 A CN200510047669 A CN 200510047669A CN 100507091 C CN100507091 C CN 100507091C
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Abstract
The present invention relates to a metal base composite material inert anode for aluminium electrolysis and its preparation method. Said inert anode is made up by using the alloy formed by using metals of iron, nickel, cobalt, chromium, titanium, copper and silver, etc. as metal phase, using metal oxides of aluminium oxide, rare earth oxide, nickel ferrite, nickel cobaltate and zinc ferrite as ceramic phase and making them undergo a synthesis process. Besides, said invention also provides the concrete steps of its preparation method.
Description
One, technical field: the present invention relates to Non-ferrous Metallurgy fused salt electrolysis field, particularly relate to a kind of anode that aluminium electrolytic industry uses and preparation method thereof for preparing.
Two, background technology: Hall-Ai Lufa that the aluminum current electrolytic industry adopts, anode all is a carbon annode, also is graphite anode, and during electrolysis, anode carbon is oxidized and consume, and electrode reaction is: Al
2O
3+ 1.5C=2A1+1.5CO
2, in addition, anodic gas secondary reaction: C+CO
2=2CO consumes more multianode carbon, produces a large amount of poisonous CO gases.One ton of aluminium of every production consumes 333 kilograms of carbon amounts in theory, but because of the multiple factor affecting of reality, the actual consumption of aluminium manufacturer about 500～600 kilograms, because of high quality carbon cellulosic material consumption increasing, price increase, the anode cost accounts for a big chunk of aluminium production cost greatly.
And the following shortcoming that existing expendable carbon annode also exists:
1, consumes a large amount of high grade coke, refinery coke;
2, a large amount of greenhouse gases and the toxic gases of discharging is as the CF of anode production process generation
4, CF
6, PNAH polynuclear aromatics, volatile organism VOC, HF, SO
x, COS and NO
x
3, anode change expense height, labour intensity are big;
4, unit production capacity one-time investment is big.
Three, summary of the invention:
1, goal of the invention: the invention provides a kind of preparation method of metal-base composite material inert anode for aluminium electrolysis, its objective is solution at present in electrolytic industry, the expendable carbon annode of use, consume big, pollute big, the problem that cost is high.
2, technical scheme: the present invention is achieved through the following technical solutions:
A kind of metal-base composite material inert anode for aluminium electrolysis, anode material are that single metal or alloy mixes the matrix material that forms with metal oxide, it is characterized in that: the metal ingredient of this material accounts for the mass percent of inert anode material formation more than 50%; Wherein: single metal or alloy is made of iron, nickel, cobalt, chromium, titanium, copper or their alloy, and alloy comprises binary alloy, the ternary alloy of iron, nickel, cobalt, chromium, titanium, copper; The metal oxide that adopts be nickel ferrite based magnetic loaded, cobalt acid nickel, zinc ferrite respectively with aluminum oxide, rare earth oxide in one or both formations.
The content of anode material is respectively: single metal or alloy mass percent 51%～90%, the mass percent 5%～41% of nickel ferrite based magnetic loaded, cobalt acid nickel, these metal oxides of zinc ferrite, one or both mass percents 1%～10% in aluminum oxide, the rare earth oxide.
The quality percentage composition of single metal or alloy is greater than 50%; The quality percentage composition of metal oxide is less than 50%.The scope of the quality percentage composition of described single metal or alloy is 51%～85%; The quality percentage composition scope of described metal oxide is 15%～38%.
A kind of metal-base composite material inert anode for aluminium electrolysis preparation methods, it is characterized in that: behind the abundant ball milling of single metal or alloy and oxidate powder, mix and be incorporated under the binding agent effect, normal temperature is colded pressing synthetic, and sintering prepares anode in the oxidesintering temperature range, does not reach composition sintering temperature difference equally, generally between 1100 ℃-1600 ℃, during sintering, the dividing potential drop of control oxygen is 1kPa～10kPa.
Metal powder or metal alloy powder, granularity reaches 200 orders behind the ball milling; Make granularity reach 5～45 μ m behind nickel ferrite based magnetic loaded, cobalt acid nickel, ferrous acid zinc powder, aluminum oxide, the rare earth oxide ball milling.
Behind the abundant ball milling of single metal or alloy and oxidate powder, alloy powder and metal oxide thorough mixing, 1000 ℃～1300 ℃ direct heat are molded.
3, advantage and effect:
Patent name is " a kind of Fe base alumina composite material aluminum electrolysis inertia anode and preparation method thereof ", and the patent of application number " 03110863.6 " also discloses the inert anode that a kind of aluminium electrolytic industry is used.The application further improves on 03110863.6 basis, because nickel ferrite based magnetic loaded, cobalt acid nickel, zinc ferrite have lower solubleness in sodium aluminum fluoride, possesses good anti-corrosion, also has simultaneously better electroconductibility, patent will directly adopt above-mentioned oxide compound to add small amounts aluminium, rare earth oxide is made ceramic phase, constitutes inert anode with metallographic phase.The effect of adding aluminum oxide and rare earth oxide is when guaranteeing that anode carries out sintering under certain oxygen partial pressure, to form the extraordinary composite oxides of a kind of antioxidant property.The anode material of this invention overcomes the nickel ferrite based magnetic loaded of the research of anode in the past and the easy embrittlement of anode material that copper forms, two shortcomings of poorly conductive.
By the enforcement of technical solution of the present invention, can solve at present in electrolytic industry the expendable carbon annode of use well, consume greatly, pollute greatly the cost height, the problem that aspects such as and existing metal matrix anode is pure conductor material preparation, consumes greatly, and over-all properties is bad exist.The present invention has following advantage:
When 1, realizing green production, by-product oxygen can produce economic benefit;
2, cooperate wettable negative electrode can significantly reduce bath voltage, realize energy-saving effect.
Anode material of the present invention prepares under the situation that certain oxygen is pressed, it is a semiconductor material, the anode material of the purer conductor of over-all properties has significantly raising, consume littler, realized the enormous benefits of energy-saving and environmental protection, unit production capacity investment, promote aluminium electrolytic industry fast, the advantage of efficient, environmental protection development.
Four, embodiment:
Anode material development of the present invention realizes by following steps and approach:
The present invention is based on some metal oxides have better erosion resistance and certain electroconductibility in the sodium aluminum fluoride-alumina high temperature fused salt of used for aluminium electrolysis oxide compound and high temperature alloy composition and be compounded to form a kind of material, after the technologies such as this matrix material process sample preparation, sintering, can apply to aluminium electrolytic industry and use as anode.On the basis of declaring patent 0311863.6, the present invention further improves on its basis, by adding nickel ferrite based magnetic loaded, cobalt acid nickel or zinc ferrite, making the metal oxide that adopts in the ceramic phase most of is nickel ferrite based magnetic loaded, cobalt acid nickel or zinc ferrite, they respectively with the aluminum oxide of small part, in the rare earth oxide one or both, in certain oxygen partial pressure atmosphere, form matrix material during sintering and make anode, improve the anodic over-all properties, make the anode material sintering temperature further reduce simultaneously, be easier to industrialization.
Anode material of the present invention is made, cold press process comprise get the raw materials ready, batch mixing, moulding, four steps of sintering, pressure sintering comprise get the raw materials ready, batch mixing, hot-forming three steps.
Get the raw materials ready: metal powder or metal alloy powder (Cu, Fe, Ni, Co, Ti or their alloy), ball milling 48 hours reaches 200 order granularities, ball: material: ethanol=2:1:1; Nickel ferrite based magnetic loaded NiFe
2O
4, cobalt acid nickel Co
2O
4, zinc ferrite ZnFe
2O
4, powder such as aluminum oxide, rare earth oxide through ball milling 72 hours so that granularity reaches 5～45 μ, ball: material: deionized water=3:1.5:1.
Batch mixing:, placed 20 hours as the even batch mixing of binding agent with water or polyvinyl alcohol oven dry back.
Moulding: normal temperature 100-400MPa coldmoulding.
Sintering: after the sample seasoning at normal temperatures of colding pressing, sintering is one to three hour in the inert atmosphere silicon molybdenum stove in sintering range or in the atmosphere control stove that certain oxygen is pressed, then under similarity condition with the furnace temperature cool to room temperature.Wherein the oxygen control of pressing constitutes mutually with different metal and changes to some extent, generally at 1kPa～10kPa.
When adopting the hot pressing straight forming, 1000 ℃-1300 ℃ of hot pressing temperatures.
Below list embodiment, so that effect of the present invention to be described.
Embodiment 1:
Get ferrous acid nickel powder 26 grams, ferric oxide 2 grams, aluminum oxide powder 2 grams, alloy 60 grams (Fe:Ni:Cu=4:3:1), make anode as stated above, do negative electrode, at 900 ℃ with graphite, carried out 16 hours electrolysis under 1.0 amperes of every square centimeter of conditions of anodic current density, ionogen is NaF-AlF
3-NaCl-CaF
2-Al
2O
3, NaF/AlF wherein
3Mole is than 2.0, and alumina concentration is 3.0wt%.During electrolysis, the vertical plumbago crucible that is added with the corundum liner, 4 centimetres of the pole spans of inserting of anode and cathode.Test result shows that the electrolytic process groove is steady, and groove is pressed 5.0 volts, and the aluminium quality product that electrolysis obtains reaches 98.3%.Anodic year, erosion rate was 18mm/a.
Embodiment 2:
Get ferrous acid nickel powder 12 grams, zinc ferrite 8 grams, aluminum oxide powder 4 grams, alloy 80 gram (Fe: Ni=4: 3), method by above-mentioned introduction makes anode, does negative electrode with graphite, at 900 ℃, carried out 12 hours electrolysis under 1.0 amperes of every square centimeter of conditions of anodic current density, ionogen is NaF-AlF
3-NaCl-CaF
2-Al
2O
3, NaF/AlF wherein
3Mole is than 2.0, and alumina concentration is 3.0wt%.During electrolysis, the vertical plumbago crucible that is added with the corundum liner, 4 centimetres of the pole spans of inserting of anode and cathode.Test result shows that the electrolytic process groove is steady, and groove is pressed 4.9～5.1 volts, and the aluminium quality product that electrolysis obtains reaches 98.8%, anodic year erosion rate be 19mm/a.
Embodiment 3:
Get ferrous acid nickel powder 40 grams, aluminum oxide powder 9 grams, CeO
2Powder 1 gram, alloy 60 grams (Fe:Ni:Co=4:3:1) make anode as stated above, do negative electrode with graphite, at 940 ℃, have carried out 10 hours electrolysis under 1.0 amperes of every square centimeter of conditions of anodic current density, and ionogen is NaF-AlF
3-CaF
2-Al
2O
3, NaF/AlF wherein
3Mole is than 2.1, and alumina concentration is 3.5wt%.During electrolysis, the vertical plumbago crucible that is added with the corundum liner, 4 centimetres of the pole spans of inserting of anode and cathode.Test result shows, the electrolytic process groove is pressed 5.0 volts, and the aluminium quality product that electrolysis obtains reaches 99.0%, anodic year erosion rate be 18mm/a.
In the electrolytic process, produce a large amount of gas around the anode,, discharge O according to anode construction composition and electrolytical composition
2, after electrolysis finished, the anodic corrosion degree was very little, and it is littler to be exposed to airborne anodic oxidation corrosion.
In sum, when the alloying constituent in the made anode material greater than 50% the time, conductivity of electrolyte materials, heat-shock resistance are enhanced, by partial oxidation aluminium, rare earth oxide are added to nickel ferrite based magnetic loaded, cobalt acid nickel, zinc ferrite is main ceramic phase, reduced the erosion rate of material, and be improved with the quality product that the production of this material obtains.
Claims (4)
1, a kind of metal-base composite material inert anode for aluminium electrolysis, anode material is that single metal or alloy mixes the matrix material that forms with metal oxide, it is characterized in that: the metal ingredient of this material accounts for the mass percent of inert anode material formation more than 50%; Wherein: single metal or alloy is made of iron, nickel, cobalt, chromium, titanium, copper or their alloy, and alloy comprises binary alloy, the ternary alloy of iron, nickel, cobalt, chromium, titanium, copper; The metal oxide that adopts be nickel ferrite based magnetic loaded, cobalt acid nickel, zinc ferrite respectively with aluminum oxide, rare earth oxide in one or both formations.
2, a kind of metal-base composite material inert anode for aluminium electrolysis according to claim 1, it is characterized in that: the content of anode material is respectively: single metal or alloy mass percent 51%～90%, the mass percent 5%～41% of nickel ferrite based magnetic loaded, cobalt acid nickel, these metal oxides of zinc ferrite, one or both mass percents 1%～10% in aluminum oxide, the rare earth oxide.
3, a kind of metal-base composite material inert anode for aluminium electrolysis according to claim 1 is characterized in that: the quality percentage composition of single metal or alloy is greater than 50%; The quality percentage composition of metal oxide is less than 50%.
4, a kind of metal-base composite material inert anode for aluminium electrolysis according to claim 3 is characterized in that: the scope of the quality percentage composition of described single metal or alloy is 51%～85%; The quality percentage composition scope of described metal oxide is 15%～38%.
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| CN101586250B (en) * | 2009-06-10 | 2010-12-29 | 中南大学 | Composite coating, preparation method and application thereof |
| CN101586246B (en) * | 2009-07-07 | 2011-01-05 | 中南大学 | High temperature resistant molten salt corrosion ceramet anode material and preparation method thereof |
| CN101736368B (en) * | 2010-01-13 | 2011-07-20 | 北京科技大学 | Noble metal ceramic composite coating inert anode for aluminum electrolysis and preparation method thereof |
| CN102011144A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer |
| CN102603341B (en) * | 2012-04-09 | 2013-06-05 | 武汉科技大学 | Fusion cast corundum-spinel brick for side wall of aluminum electrolytic bath and preparation method of fusion cast corundum-spinel brick |
| CN105452538B (en) * | 2013-08-19 | 2018-02-02 | 俄铝工程技术中心有限责任公司 | For obtaining the iron-based anode of aluminium by being electrolysed melt |
| CN103710728A (en) * | 2013-12-11 | 2014-04-09 | 中国铝业股份有限公司 | Method for connecting ceramic alloy outer shell and metal inner core for metal molten salt electrolysis |
| CN104047035A (en) * | 2014-06-27 | 2014-09-17 | 中国铝业股份有限公司 | Inert anode for fused salt electrolysis and preparation method thereof |
| CN104291385B (en) * | 2014-08-26 | 2016-05-25 | 江苏合志锂硫电池技术有限公司 | Cobalt acid nickel mesoporous microsphere and preparation method thereof |
| CN109468667B (en) * | 2019-01-16 | 2020-04-21 | 江西理工大学 | Lead-zinc ferrite composite anode for zinc electrodeposition and preparation method thereof |
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