CN101024887A - Method for preparing MnO2 doped aluminium-base metal ceramic inert anode - Google Patents
Method for preparing MnO2 doped aluminium-base metal ceramic inert anode Download PDFInfo
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- CN101024887A CN101024887A CN 200710013048 CN200710013048A CN101024887A CN 101024887 A CN101024887 A CN 101024887A CN 200710013048 CN200710013048 CN 200710013048 CN 200710013048 A CN200710013048 A CN 200710013048A CN 101024887 A CN101024887 A CN 101024887A
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Abstract
The invention provides a MnO2 doped aluminum oxide base metal ceramic inert anode preparing method, characterized in adopting the following steps of: (1) proportioning raw materials: on the basis of a mixture of Fe-Ni metal powder in 50wt%-80wt% and aluminum oxide powder in 20wt%-50wt%, adding in MnO2 powder in 1%-5% of total weight of the mixture; (2) mixing Fe-Ni metal powder, aluminum oxide powder and MnO2 powder and placing them in a grinding jar for grinding into particles able to pass through 250-mesh sieve, then adopting powder metallurgy to make cold press molding to prepare metal ceramic inert anode material and dry it; (3) burying aluminum oxide and sintering in a Si-Mo furnace charged with Ar gas at 1450-1550 deg.C for 2-3 h; (4) lowering the temperature in the Si-Mo furnace under the protection of Ar gas at a rate <=5deg.C/min to the room temperature and obtaining MnO2 doped aluminum oxide base metal ceramic inert anode material where Mn enters Al site to form spinel solid solution. And the anode material has features of high compactness, good conductivity and corrosion resistance, and being good for aluminum electrolysis.
Description
Affiliated technical field
Patent of the present invention provides a kind of MnO
2The preparation method of doped aluminium-base metal ceramic inert anode belongs to the material technology field.
Background technology
Two patents of Hall in 1886 and Herout have been established since the basis of modern aluminum industry, and sodium aluminum fluoride-alumina molten salt electrolysis method always is the unique metallurgy method for aluminum of aluminium industry, and current electrolysis aluminium industrial production adopts carbon pole to have many shortcomings.Direct current is in the anode lead-in groove in the aluminium cell, through electrolyte layer, derives from negative electrode, and electrochemical reaction takes place on anode-electrolyte interface, produces CO
2With CO gas, on negative electrode-electrolyte interface, produce liquid aluminium, electrolysis temperature is generally 950～970 ℃.And anode is electrolytic heart, and traditional aluminium cell adopts the deflection type carbon annode, and the anode expense accounts for about the 5-20% of Aluminum Electrolysis Production cost, and seriously polluted, produces greenhouse gases CO
2With CO gas, so the research of aluminum electrolysis inertia anode (claiming not consumable anode again) is significant.
From eighties in 20th century particularly after the nineties, the research of aluminum electrolysis inertia anode mainly concentrates on metal anode, sintering metal, these a few class materials of oxide anode.Because ceramic-metal composite corrosion resistance in the ionogen fused salt is good, metallic matrix also has bonding and electroconductibility excellent function simultaneously, the research of cermet inert anode in recent years becomes focus, the many wustite spinel-like type compounds with nickel, cobalt, zinc of research are matrix, the little metal phase (mainly contains Cu, Ag or its alloy etc.) constitute, and no matter ceramic phase is static corrosion or electrolytic corrosion, all be chemical dissolution and physical dissolution process, the dissolving of electrode must impact the purity of electrolytic aluminum.
Ceramic-metal composite is the matrix material of metal and oxide ceramics, has merged the anti-oxidant high-temperature stability of the good conductivity and the oxide ceramics of metal, makes it be more suitable for doing the aluminum electrolysis inertia anode material.Generally Yan Jiu sintering metal is by NiO that contains the copper base metal phase and NiFe
2O
4Form, it has pottery (anticorrosive and oxidation) and metal good electrical conductivity and heat-shock resistance concurrently) advantage.Oxide matrix provides an anticorrosive net that comprises electric conductor copper base metal phase, can form layer protecting film when metallographic phase polarizes, and makes metal anode avoid electrolytical corrosion.Such sintering metal anode is measured at 0.0015 and 0.0005cm/h respectively in the anticorrosive rate of the high-temperature systems of ice crystal ground mass and sodium aluminum fluoride-aluminum oxide cryogenic system.1993, about using NiFe
2O
4Base inert anode in the experimental study of 6KA electrolyzer be seen in document (" MaterialsCharacterization of Cermet Anodes Tested in a Pilot Cell ". be published in " Light Metals ", 1993:445-454).The anode that experiment is adopted consists of 42.9%NiO-40.1%Fe
2O
3-17%Cu is at the synthetic NiFe of 980 ℃ of following sintering
2O
4Mix with Cu the back, and behind cold press and sintering, the anode extrudate density that obtains is 6.0g/cm
3The anode diameter that current experiment is adopted is 15.24cm, and anode rod adopts Stainless Steel Alloy.In order to improve the anodic solidity to corrosion, high molecule ratio ionogen (CR=3) and the close (～0.5A/cm of low current have been adopted
2) wait measure, so that electroconductibility and solidity to corrosion are further improved.Anode is investigated with problems such as being connected of guide rod the operation of electrolyzer, the quality and the electrode of primary aluminum through 614 hours experiment.The subject matter that experiment exposes is that large size anodic shock resistance is poor, the face of electrode erosion property is still waiting to improve the well damage of conducting rod etc.In addition, Fe
2O
3Solubleness in cryolite fused salt is bigger, makes that finally the purity of product aluminium is low.
People such as V.Blinov had studied NiFe in 1997
2O
4-18%CuO-17%Cu is applied to test (" the Behaviour of inert anodes for aluminiumelectrolysis in a low temperatureelectrolyte of low-temperature electrolytic aluminium production aspect, part I " be published in " Aluminium ", 1997,73 (12): 906-910), the ionogen that they select is BaF
2-NaF-AlF
3-Al
2O
3, service temperature is 800 ℃, anodic current density is 0.2A/cm
2, behind 134 hours electrolytic trial, find same oxide ceramics electrode in 800 ℃ of low-temperature aluminum electrolysis matter than corrosion in 950 ℃ of industrial aluminum ionogen slowly many, but same anode dimension can not be done too greatly, otherwise corrodes very soon.Yao Guangchun etc. have carried out studying (seeing " MnO to the corrosion resistance nature that improves the spinel based inert anode of ferronickel with regard to additive
2To ferronickel spinel inert anode material Effect on Performance ", be published in " functional materials " .2005.36 (3): 374-376.), point out MnO
2Can acceleration of sintering, improve the density of goods, and can improve the resistance to corrosion of goods, add 1%MnO
2The corrosion rate of back sample is 1/7 of a pure spinel sample.Sample is found through X-ray diffraction analysis, adds MnO
2MnO appears in the no cenotype in back
2With NiFe
2O
4Form Solid solution, Mn
4+Ionic replacement part Fe
3+Ion, material are still the ferronickel spinel structure, and add 2%MnO
2The static heat erosion rate of inert anode sample minimum, the influence of additive to specific conductivity is not discussed in the document.
The loyal peaceful grade of stone is studied the metal-aluminum oxide ceramic anode and (is seen " used for aluminium electrolysis Fe-Ni-Co-Al
2O
3Cermet inert anode "), be published in " China YouSe Acta Metallurgica Sinica ", 2004,5, Vol.14 S1:36～40.), and develop nickel aluminate and Fe-Ni-Co-Al-0 inert anode.960 ℃ of electrolysis temperatures, aluminum oxide quality concentration is 6.0%, and anodic current density is 1.0A/cm
2, molecular ratio is in 2.6 the ionogen it have been carried out the electrolysis of 10h.Electrolytic process is steady, and the electrolytic aluminum product purity reaches 96%～99%, and this anode possesses electroconductibility, anti-oxidant and erosion resistance preferably.Adopt X-ray diffraction and electro-probe micro analyzer (EPMA) that the anode after the electrolysis is analyzed, find that there are spinel type compounds such as nickel ferrite based magnetic loaded, iron aluminate could in anode surface, anode surface lower floor is ceramic phase and metallographic phase such as iron aluminate could, cobalt acid nickel; The mutual disperse of metallographic phase and ceramic phase distributes and constitutes the cermet coating of compact structure, thinks approaching the theoretic requirement that the performance of prepared noble electrode has, year an erosion rate be 23.91mm/year.Still do not solve corrosion-resistant and problem electroconductibility.
The problem that exists in the present above-mentioned technology is electroconductibility and erosion resistance, not only to possess stronger corrosion resistance nature as the inert anode in the electrolyzer, also to possess conductivity preferably simultaneously, and electroconductibility should not be too big with variation of temperature, otherwise can limit the raising of anodic current density, sometimes also can concentrate because of local current, and cause crackle in the contact position of anode and current conducting rod.
Summary of the invention
The good MnO of purity, use properties that provides a kind of needs that can overcome above-mentioned defective, be fit to electrolysis of aluminum at present, guarantees product aluminium of the present invention
2The preparation method of doped aluminium-base metal ceramic inert anode.Its technical scheme is:
A kind of MnO
2The preparation method of doped aluminium-base metal ceramic inert anode, it is characterized in that adopting following steps: (1) proportioning raw materials, in weight ratio is that other adds 1%～5%MnO of amount of the mixture on the basis of iron nickel metal powder 50～80% and aluminum oxide powder 20%～50% mixture
2Powder; (2) with iron nickel metal powder, aluminum oxide powder and MnO
2Powder mixes in the grinding pot of packing into and is ground to by 250 mesh sieves, adopts powder metallurgy process coldmoulding then, is prepared into the cermet inert anode material, and oven dry; (3) in the silicon molybdenum stove that feeds argon gas atmosphere, buried the aluminum oxide powder sintering 2～3 hours at 1450～1550 ℃; (4) temperature in the silicon molybdenum stove is reduced to room temperature with the cooling rate of≤5 ℃/min under argon shield, promptly gets MnO
2Doped aluminium-base metal ceramic inert anode material, its composition are that manganese enters the aluminium position, form spinel solid solution.
Described MnO
2The preparation method of doped aluminium-base metal ceramic inert anode, in the step 1, the weight ratio 1～5: 3 of iron and nickel in the iron nickel metal powder.
Described MnO
2The preparation method of doped aluminium-base metal ceramic inert anode, in the step 2, the coldmoulding pressure for preparing the cermet inert anode material with powder metallurgy process is 40-160Mpa.
The present invention compared with prior art has following advantage:
1, adopts MnO
2Doping process adds MnO in the experimental raw
2After, owing in the sintering process Mn can take place
4+Replace A1
3+Cause positively charged ion vacancy defect in the lattice, the spread coefficient of material is proportional with relevant defect density in the solid-phase sintering process, the elimination of pore has been quickened in the increase of spread coefficient, thereby help sintering, the density that shows sample increases, void content reduces, and the material density height that obtains adds MnO
2Back material microstructure changes, and fine and close more, grain growing is complete, and crystal boundary reduces, and electronics wants to finish the conducting process in polycrystalline material, just must pass through crystal boundary, overcomes the crystal boundary potential barrier, so material has good electrical conductivity and erosion resistance;
2, adopt more metal powder, metal is bonded together alumina-ceramic, becomes a strong structure, and the metallographic phase dispersivity is good, forms network structure, not only can the mitigate corrosion degree, can also improve its electroconductibility;
3, ceramic phase is an aluminum oxide in the sintering metal, and the raw material of electrolysis of aluminum is an aluminum oxide, so even the ceramic phase aluminum oxide is dissolved in the fused salt, also can the purity of electrolytic aluminum not exerted an influence, is fit to the needs of electrolytic aluminum.
Embodiment
Embodiment 1:
(1) proportioning raw materials, the weight ratio of iron and nickel is 2: 3 in the iron nickel metal powder, is that other adds the MnO of above-mentioned amount of the mixture 1% on the basis of iron nickel metal powder 50% and aluminum oxide powder 50% mixture in weight ratio
2Powder; (2) with iron nickel metal powder, aluminum oxide powder and MnO
2Powder mixes in the grinding pot of packing into and is ground to by 250 mesh sieves, adopts powder metallurgy process 40Mpa coldmoulding then, is prepared into the cermet inert anode material, and oven dry; (3) in the silicon molybdenum stove that feeds argon gas atmosphere, buried the aluminum oxide powder sintering 2 hours at 1550 ℃; (4) temperature in the silicon molybdenum stove is reduced to room temperature with the cooling rate of≤5 ℃/min under argon shield, promptly gets MnO
2Doped aluminium-base metal ceramic inert anode material, its composition are that manganese enters the aluminium position, form spinel solid solution.Through scanning electron microscopic observation, grain growing is complete, and the density height is through recording sample apparent density 4.71g/cm
3, good through recording sample erosion resistance and conductivity, annual corrosion rate is 13mm/year, specific conductivity is 67S/cm under 900 ℃ of temperature.
Embodiment 2:
(1) proportioning raw materials, the weight ratio of iron and nickel is 4: 3 in the iron nickel metal powder, is that other adds the MnO of amount of the mixture 2% on the basis of iron nickel metal powder 70% and aluminum oxide powder 30% mixture in weight ratio
2Powder; (2) with iron nickel metal powder, aluminum oxide powder and MnO
2Powder mixes in the grinding pot of packing into and is ground to by 250 mesh sieves, adopts powder metallurgy process 160Mpa coldmoulding then, is prepared into the cermet inert anode material, and oven dry; (3) in the silicon molybdenum stove that feeds argon gas atmosphere, buried the aluminum oxide powder sintering 2 hours at 1450 ℃; (4) temperature in the silicon molybdenum stove is reduced to room temperature with the cooling rate of≤5 ℃/min under argon shield, promptly gets MnO
2Doped aluminium-base metal ceramic inert anode material, its composition are that manganese enters the aluminium position, form spinel solid solution.Through scanning electron microscopic observation, grain growing is complete, and the density height is through recording sample apparent density 5.45g/cm
3, good through recording sample erosion resistance and conductivity, annual corrosion rate is 12mm/year, specific conductivity is 79S/cm under 900 ℃ of temperature.
Embodiment 3:
(1) proportioning raw materials, the weight ratio of iron and nickel is 5: 3 in the iron nickel metal powder, is that other adds the MnO of amount of the mixture 3.5% on the basis of iron nickel metal powder 80% and aluminum oxide powder 20% mixture in weight ratio
2Powder; (2) with iron nickel metal powder, aluminum oxide powder and MnO
2Powder mixes in the grinding pot of packing into and is ground to by 250 mesh sieves, adopts powder metallurgy process 40Mpa coldmoulding then, is prepared into the cermet inert anode material, and oven dry; (3) in the silicon molybdenum stove that feeds argon gas atmosphere, buried the aluminum oxide powder sintering 3 hours at 1500 ℃; (4) temperature in the silicon molybdenum stove is reduced to room temperature with the cooling rate of≤5 ℃/min under argon shield, promptly gets MnO
2Doped aluminium-base metal ceramic inert anode material, its composition are that manganese enters the aluminium position, form spinel solid solution.Through scanning electron microscopic observation, grain growing is complete, and the density height is through recording sample apparent density 5.51g/cm
3, good through recording sample erosion resistance and conductivity, annual corrosion rate is 13mm/year, specific conductivity is 87S/cm under 900 ℃ of temperature.
Claims (3)
1, a kind of MnO
2The preparation method of doped aluminium-base metal ceramic inert anode is characterized in that adopting following steps:
(1) proportioning raw materials is that other adds 1%～5%MnO of amount of the mixture on the basis of iron nickel metal powder 50～80% and aluminum oxide powder 20%～50% mixture in weight ratio
2Powder; (2) with iron nickel metal powder, aluminum oxide powder and MnO
2Powder mixes in the grinding pot of packing into and is ground to by 250 mesh sieves, adopts powder metallurgy process coldmoulding then, is prepared into the cermet inert anode material, and oven dry; (3) in the silicon molybdenum stove that feeds argon gas atmosphere, buried the aluminum oxide powder sintering 2～3 hours at 1450～1550 ℃; (4) temperature in the silicon molybdenum stove is reduced to room temperature with the cooling rate of≤5 ℃/min under argon shield, promptly gets MnO
2Doped aluminium-base metal ceramic inert anode material, its composition are that manganese enters the aluminium position, form spinel solid solution.
2, MnO according to claim 1
2The preparation method of doped aluminium-base metal ceramic inert anode is characterized in that: in the step 1, and the weight ratio 1～5: 3 of iron and nickel in the iron nickel metal powder.
3, MnO according to claim 1
2The preparation method of doped aluminium-base metal ceramic inert anode is characterized in that: in the step 2, the coldmoulding pressure for preparing the cermet inert anode material with powder metallurgy process is 40-160Mpa.
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| CN 200710013048 CN101024887A (en) | 2007-01-09 | 2007-01-09 | Method for preparing MnO2 doped aluminium-base metal ceramic inert anode |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104047030A (en) * | 2014-06-27 | 2014-09-17 | 中国铝业股份有限公司 | Preparation method for aluminum electrolysis inert anode of ceramic housing and alloy inner core |
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2007
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104047030A (en) * | 2014-06-27 | 2014-09-17 | 中国铝业股份有限公司 | Preparation method for aluminum electrolysis inert anode of ceramic housing and alloy inner core |
| CN104047030B (en) * | 2014-06-27 | 2016-05-18 | 中国铝业股份有限公司 | The preparation method of the aluminum electrolysis inertia anode of a kind of ceramic package and alloy inner core |
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Open date: 20070829 |