CN101713083B - Molten-salt electrolytic aluminum inert anode, preparation method and application thereof - Google Patents
Molten-salt electrolytic aluminum inert anode, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a molten-salt electrolytic aluminum inert anode, a preparation method and application thereof, which belongs to the technical field of metal-ceramic composite materials. The inert anode is synthesized through a metal phase and an oxide phase, wherein the oxide phase consists of Al2O3, ZrO2, V2O5, CeO2 and MgO micro-powder on a nanometer and quasi-nanometer scale, and the metal phase consists of Cu, Ni, Co, Fe, Al, Mn, Zn, Cr, Ti, Nb, V, Ta and Y powder on a micron scale. The method performs wet grinding, drying and isostatic/mechanical-pressure forming on nanometer and quasi-nanometer scale oxide powder and micron-scale mixed metal powder, and then performs sintering through a vacuum/protective-atmosphere sintering furnace and machining on the obtained product in order to obtain the inert anode. The inert anode is used as a substitute for molten-salt electrolytic aluminum carbon anodes. The inert anode has the advantages that the inert anode has good conductivity and high melting point; primary aluminum products produced by electrolysis is free from anode pollution; the inert anode is high in toughness, plasticity and hot strength, good in machining performance and low in cost; the impurity content of primary aluminum meets the requirements of national standards; and the amount of anode loss is up to 22 to 25 mm/year, and the like.
Description
Technical field:
The present invention relates to a kind of molten-salt electrolytic aluminum inert anode and its production and application, belong to the ceramic-metal composite technical field.
Background technology:
Except iron and steel, aluminium is output maximum in the world, the metal that consumption is maximum.Aluminium be not only must be many production and the means of living, and be must be many strategic materials, so the production technology progress of aluminium and the reduction of production cost are the important subject that the world respectively produces aluminium big country always.
In electrolytic aluminum, except electric energy consumption, the consumption of carbon annode proportion in the electrolysis of aluminum cost is maximum (about 1600 yuan of/ton aluminium).And when carrying out electrolysis of aluminum, except continuous burning with consume the carbon annode, also produce CO simultaneously with carbon annode
2, CO and CF
4, C
2F
6And HF, SO
x, obnoxious flavour such as NOx, these discharge of harmful gases not only influence producers' health, and cause the pollution of atmospheric environment.
Nineteen nineties, at that time first produce aluminium big country (U.S.) once the someone to imagine with inert anode (be not oxidized burning in the electrolytic process, the anode that is not also corroded and consume), replace the current carbon annode that uses, this imagination is subjected to the support energetically of United States Government and aluminium enterprise, has successively invested tens dollars of development and applied researcies thereof of carrying out inert anode.
" in the aluminium technological revolution strategic planning of development " formulated in USDOE and U.S. industrial technology office
[1], the research of inert anode is placed above the other things, be the developing direction of the most important thing, the validity period of this strategic planning is the year two thousand twenty
[1]
Under the support of above-mentioned strategic planning and funds, the researchist of the U.S. has done many researchs at the material of inert anode aspect synthetic, and has delivered more patent and paper.United States Patent (USP) for example
[2]Public Fabric by multivariant oxide powder and metal-powder synthetic cermet inert anode.Wherein multivariant oxide has (NiFe
2O
4ZnFe
2O
4), (NiFe
2O
4NiO), (NiFe
2O
4ZnFe
2O
4ZnO), (ZnNi) Fe
2O
4, (ZnNi) Fe
2O
4NiO, (ZnNi) Fe
2O
4ZnO, (ZnNi) Fe
2O
4ZnONiO waits multiple combination.And can from metals such as Ni, Cu, Co, Zn, Cr, Ag, Ti, Al, Sc, Zr, No.V.Mn.Y.La, choose with above-mentioned metal oxide blended metal.Above-mentioned oxide powder is with after metal-powder mixes, through compacting be sintered into cermet inert anode.United States Patent (USP)
[3]Then reported a kind of by Fe
2O
3, NiO,
Form ceramic phase Deng oxide compound, and wherein one or both form its metallographic phase by choosing among Cu, Ag, Pd, Pt, the Au.Above-mentioned oxide powder becomes inert anode material with after metal-powder mixes through compacting sintering.
The Chinese research person has then studied automolite ZnFe in people such as advanced persons
2O
4Inert anode and CuO, CeO
2, Ni
2O
3With of the influence of additives such as ZnO to inert anode electroconductibility and erosion resistance
[4], their result of study shows, ZnFe
2O
4Cermet inert anode has good corrosion resistance to aluminium electrolyte, but the electroconductibility of this material is not good, can not be as the ideal inert anode.But add CuO, CeO
2, Ni
2O
3After oxide addition such as ZnO, then the electroconductibility of inert anode makes moderate progress, but after having added above-mentioned additive, inert anode decreases again to the erosion resistance of aluminium electrolyte.
Chinese research person Qin Qing is big, Lai Yanqing, Wu Xianxi
[5,6,7]Then studied nickel ferrite NiFe Deng the investigator
2O
4Be the cermet inert anode of base, their common ground of research is all to think NiFe
2O
4Pottery has good erosion resistance and high temperature oxidation resistance to aluminium electrolyte, during therefore synthetic inert anode all with NiFe
2O
4Make basic raw material, also in inert anode, add NiO and nickel powder for the electroconductibility that improves inert anode simultaneously
[5,6], perhaps copper powder
[7,8]These raw material powder are mixed through levigate, become cermet inert anode behind compacting and the sintering.But when carrying out electrolysis of aluminum with this class inert anode, the electroconductibility that still exposes inert anode is not good, and pollutes the product standard that impurity such as the primary aluminum iron content make the electrolysis output, copper too much can not reach electrolytic aluminum because of being subjected to inert anode material
[5,6]
In addition, no matter be the MFe that United States Patent (USP) was studied
2O
4Type, MFe
2O
4MO type and (Ni, Zn) Fe
2O
4, (Ni, Zn) Fe
2O
4ZnO, (Ni, Zn) Fe
2O
4The cermet inert anode of types such as NiO, or the Chinese research person is the ZnFe that studied
2O
4, NiFe
2O
4And Cu-NiFe
2O
4Etc. various cermet inert anodes, all have a common shortcoming, promptly thermal shock resistance is poor, this metalloid ceramic inert anode material, in the time of in adding the high temperature aluminum ionogen, make inert anode heat is cataclasm or hot cracked automatically owing near the thermal stresses the metal line is high especially
[9,10,11]This thermal shocking brittle failure problem expands pilot scale in experimental scale, or productivity single-piece when test, and problem is outstanding especially, because the cermet inert utmost point that size heals big more is easy to generate the thermal shocking brittle failure
[11]
In addition, this type oxide cermet inert anode because of can not carrying out mechanical cutting processing or welding processing, thereby is difficult to realize that anode and electrolytic conduction conflux being connected of board.
For overcoming the above-mentioned shortcoming of cermet inert anode, part American Studies person turns to again and studies the metal mold inert anode
[8,11], the xantal type inert anode of people such as the wherein the most representative person Jianhong Yang that is American Studies development
[11],, and aluminium electrolyte is also had erosion resistance preferably because xantal not only has good electroconductibility and machinable.Because the fusing point of xantal is lower than 1000 ℃, with xantal anode electrolysis aluminium, can not in conventional electrolysis matter, carry out, and can only be by AlF
3+ KF+NaF+Al
2O
3Four constituent elements are to carry out in the low melting point ionogen of leading, and keep electrolytical temperature in the electrolysis between 700-750 ℃.The result of xantal anode electrolysis aluminium test is a current efficiency 33.1～76.9%, copper content is higher in the electrolysis output aluminium, reaches 0.62% to 6.23%, has surpassed the requirement of product standard, behind 30 to 100 hours electrolytic trial, catastrophic corrosion has taken place in the xantal anode
[11]This explanation xantal anodic corrosion resistance still is unfavorable.
The performance index of inert anode should comprise following six aspects: have good electroconductibility and 1250 ℃ and above fusing point; Under electrolysis high temperature, anode material does not dissolve in electrolysis of fluorides matter and its component is not polluted the primary aluminum product of electrolysis output; Under electrolytic high temperature, the nascent oxygen atom oxidation that not produced by anode; Have certain high temperature toughness plasticity and hot strength, brittle failure does not take place under the impact of high temperature rapid heat cycle; But the performance with mechanical cutting processing or welding processing can link to each other with the electrolytic conduction board that confluxes; Can easily produce large-scale aluminium required large size of industry and large batch of anode, and the cost of material is low.Present proprietary concentrate, no any above-mentioned six requirements of satisfying simultaneously.
Reference:
[1]Ross?Brindle，Nancy?Margolis：“Stragy?for?Technology?Innovation?in?theu.s.Aluminium?Industry”，(U.S.Department?of?Energy，office?of?IndustrialTechnology)。
[2]Xinghua?Liu，Siba?P.Ray，Alfred?F?et?al：“U.S.patent.7014881?B2.(Mar.21.2006)”.
[3]Siba?P.Ray，Xinghua?Liu?and?Douglass.A：“U.S.pateut6372.119?B1(Apr.21.2006)”。
[4]Yu?Xiao-jin，Zhang?Guang-Li?and?Qiu?Zhu-xian：“Electro?conductivity?andcorrosion?Resistance?of?ZnFe
2O
4-Based?Materials?used?as?Inert?Anode”(J).Journalof?ShangHai?university.Vol.3.NO.3.sept.1999。
[5]Qin?Qing-wei，Lai?Yan-qing?and?Xiao?Jin：“preliminary?testing?of?NiFe
2O
4-NiOas?ceramic?matrix?of?cermet?inert?anode”(J)，Trans.Nonferrous?Met.Soc.China.Vol.13.NO.5.oct.2003。
[6] Lai Yanqing, Huang Wei, field faithful and upright person etc.: " electrolysis of aluminum NiFe
2O
4The progress of base metal ceramic inert anode performance "
(J) " mineral products protection and utilization " NO.4.Aug.2006.
[7] Wu Xianxi, Xu Lihua, Zhang Licheng: " preparation of the large-scale cermet inert anode of electrolysis of aluminum and electrolysis test "
(J) " Guizhou University of Technology's journal " the 6th phase in 2006.
[8] Liu Wei, Liu Jingmei, Zhang Licheng: " large-scale aluminium is separated the development of inert anode " be " light metal " (J).2006. the 5th phase.
[9]J?Li，Q.S.Zhang，and?Y.Q.Lai：“Thermal?stresses?Relaxation?Design?ofNi/NiFe
2O
4?Graded?cermet?Inert?Anode”[J]，“Act.Metallurgica?Sinica”.vol.18，NO.5.2005。
[10] Lv Zijian: " to the selection of aluminum electrolysis inertia anode and the thinking of research direction." [J], the 10th phase of " light metal " .2003.
[11]Jianhong?Yang，John?N.and?N.Hyrn：“Aluminum?Electrolysis?Tests?withinert?Anode?in?KF-AlF
3-Based?Electrolysis”(J)，“Light?Metals”2006，Edited?byTravis?J.Galloway?TMS。
[12] Qiu Zhuxian writes: " electrolysis of aluminum " (M). metallurgical industry press (nineteen ninety-five).
Summary of the invention:
The objective of the invention is to overcome the deficiencies in the prior art, and a kind of molten-salt electrolytic aluminum inert anode that can satisfy the every performance index of molten salt electrolysis of metals inert anode and its production and application is provided.
In order to make the inert anode of developing have the performance of good electrical conductivity and corrosion of high temperature resistance melt and oxidation.Inert anode material of the present invention has following three essential distinctions with the inert anode of being studied both at home and abroad: the one, and oxide ceramics main composition mutually is Al
2O
3, the remarkable advantage of composition design is like this, in aluminium electrolysis process, even the anode composition has a spot of dissolving, also can not pollute the electricity product and separate the primary aluminum of output; The 2nd, adopt the multicomponent oxide ceramic phase, so that make the inert anode of developing have many-sided over-all properties, as containing ZrO in the ceramic phase
2And V
2O
5, ZrO
2Can make the hot strength and the toughness of ceramic phase improve a lot V
2O
5The electroconductibility of ceramic phase is significantly increased; Contain CeO in the ceramic phase
2, the electroconductibility of ceramic phase is significantly increased; Contain MgO in the ceramic phase, make ceramic phase behind sintering, have fine grain fineness number and the physical strength of Geng Gao; The 3rd, allocate the oxide compound of inert anode into, reach nanometer and quasi-nano is other through high-energy ball milling, because it is different with carbide cermet, oxide compound and metal are to be difficult to form the desired metallic pottery, and not only wettability is very poor mutually because metallographic phase is with oxide compound, and the coefficient of expansion between the two differs greatly, these differences not only make mixing that metallographic phase and ceramic phase can not be good, thereby cause the difficulty that is shaped, and the material base that has been shaped is easy to generate crackle and disrumpent feelings when sintering.When the mixed oxide of allocating inert anode into reach nanometer and quasi-nano not after, utilize the low melting point effect and the surfactivity effect of nanometer powder, will make metallographic phase and oxide ceramics wettability and the consistency between mutually obtain significantly to improve.Inert anode is shaped easily, and inert anode also is difficult for cracking with disrumpent feelings after sintering, electroconductibility and high-temperature mechanical property also obtain remarkable improvement.
The present invention implements like this:
1, the raw material of inert anode is formed: inert anode material of the present invention, to form by oxide ceramics phase and metallographic phase, and the biphase weight percent is: metal: oxide compound=(25～50): (75～50).Wherein oxide compound is mutually again by Al
2O
3, ZrO
2, V
2O
5, CeO
2Reach compositions such as MgO, the weight percent of five constituent element oxide compounds is: Al
2O
3: ZrO
2: V
2O
5: CeO
2: MgO=(90～71): (5～15): (2～6): (2～5): (1～3).Metallographic phase in the inert anode is selected 5 to 7 kinds from following 13 kinds of metals; Cu, Ni, Co, Fe, Al, Zn, Mn, Cr, Ti, Nb, V, 13 kinds of Ta and Y etc.The various oxide compounds and the metal that are added are the technical pure meal, and powder size is between 80～300 orders, and various oxide compound meal or metal meal are all bought from market.
2, the preparation method of inert anode
The preparation method of inert anode is divided into two stages as Fig. 1 with shown in the technical process of Fig. 2.Be specially:
Fs is for producing mixed oxide nanoparticle and accurate ground rice end (shown in Figure 1).Take by weighing various oxide compound coarse meals by weight percentage, use mechanical or manual mixing,, put into the ball milling that high energy ball mill carries out 20-26 hour at 900-1000 ℃ of temperature lower calcination 4-6 hour.High energy ball mill can be vertical or horizontal stirring mill, and the processing parameter of high-energy ball milling is: ball material weight ratio is no less than 6, and mixing speed is no less than 100 rev/mins.Abrading-ball is 4,6,8,16 by diameter, and other Wimet abrading-ball of five kinds of levels of 25mm is formed.Through the mixed powder of high-energy ball milling, its granularity is 80～200nm, as shown in Figure 3.
Subordinate phase is preparation inert anode (shown in Figure 2), and preparation inert anode technology is four steps:
The first step is equipped with mixed powder for the general milling legal system, the mixed oxide nanoparticle of predetermined weight/accurate nanometer powder and mixed metal powder and dispersion agent, binding agent and surface-modifying agent, together adds in the ball mill, is no less than 8 hours ball milling.General milling not only has mixing and grinds two kinds of effects, metal and oxide compound powder mix through ball milling more than 8 hours, not only play further levigate effect, and facilitate interosculating of metal powder and oxidate powder, accurate nanometer of the oxide compound of part high rigidity and nano powder, under the effect of mechanical force, embed in the more coarse-grained metal powder granulates, prevented the segregation of metal powder and oxidate powder.Forcibly improved the wettability between metal and the oxide compound.After adding surface-modifying agent and dispersion agent, prevent the reunion of nanometer and accurate nano powder, surface-modifying agent is with primary alconol HO-R or oleic acid, add-on be compound heavy 0.5～1.0%.Dispersion agent is industrial spirit or distilled water or pure water.Binding agent is a polyvinyl alcohol, polyvinyl alcohol, polyethylene polymer, polyoxyethylene glycol, polycarbonate, polyvinyl acetate, carboxymethyl cellulose.The add-on of binding agent is that metal mixes 3～7% of grain weight with oxide compound.Binding agent added in the general milling discharging in preceding two hours.
Second step was cryodrying, and moisture content or the alcohol of its purpose in removing compound prevents in molded, produced material and extruded from the slit of mould.The temperature of cryodrying is 80～120 ℃, and the exsiccant time is then according to what of inventory, and the thickness of the bed of material and deciding is generally at 6-10 hour.
The 3rd step is for molded: with the moulding of metal pattern mechanical pressure, or use the rubber mold hydrostatic pressing.Forming pressure is 150～250Mpa.Different according to inert anode shape and dimensional requirement become conventional different shape to the die design that is pressed into shaping, as cylindric, and rectangular column or tabular etc.
The 4th step was the sintering of shaping blank: blank is sintering in vacuum sintering furnace or protective atmosphere high temperature sintering furnace.The protective atmosphere sintering is fit to purity 99.99% argon shield, and vacuum sintering is 10
-1～10
-2Sintering under the vacuum tightness of Pa.Sintering temperature is 1250-1450 ℃, keeps 90-150 minute under sintering temperature, finishes sintering.The length or the radial shrinkage ratio of column sample are 74～76% before and after the sintering.
The 5th step is for lathing and process screw thread finishing the agglomerating inert anode, so that link to each other with the electrolytic conduction board that confluxes.Connecting thread photo when Fig. 4 is lab scale after the column inert anode turning processing.
The present invention compares with the domestic and international similar technology of studying, have anode conducting and reach the fusing point height well, the performance of high temperature resistance dielectric corrosion and oxidation is good, and is pollution-free to the primary aluminum product of electrolysis output, toughness plasticity and hot strength height, and can carry out mechanical workout, be connected with the board that confluxes, cost is low, and the foreign matter content of primary aluminum reaches the GB requirement, the anodic waste reaches 22-25mm/, can replace present electrolytic aluminum carbon annode.
Description of drawings:
Fig. 1 is polynary mixed oxide batching and the process flow sheet that is processed into nanometer powder.Contain calcining and high-energy ball milling two-step.
Fig. 2 is for being processed into the process flow sheet of inert anode by polynary mixed oxide nanoparticle/accurate nanometer powder and metal-powder, its master operation is the sintering that is pressed into shape and sample of sample.
Fig. 3 for multivariant oxide through becoming the scanning electron microscope picture of nanometer/accurate nanometer behind the high-energy ball milling.
But Fig. 4 is for process agglomerating column inert anode and cut out connecting thread profile photo.
Fig. 5 is a high temperature fused salt electrolysis aluminium experimental cell structural representation, and 1 is inert anode among the figure; 2 is plumbago crucible, also is the negative electrode of electrolyzer simultaneously; 3 is screwed conductive copper bar, and bolt screws in the sidewall of plumbago crucible; 4 for having TiB
2The graphite cathode of coating; 5 are corundum insulation inner sleeve; 6 is the fused electrolyte molten bath.
Embodiment:
Embodiment 1: the weight percent of inert anode ceramic phase consists of Al
2O
3: ZrO
2: V
2O
5: CeO
2: MgO=90: 5: 2: 2: 1.Metallographic phase with oxide compound weight percent mutually is: ∑ oxide compound: ∑ metal=50: 50.Metallographic phase is made up of Cu, Al, Ni, Ti, Ta five elements.The weight percent of each element is Cu: Al: Ni: Ti: Ta in the metallographic phase :=60: 20: 10.6: 4:.Each constituent element in ceramic phase and the metallographic phase is allocated into by micron-sized powder.Anode preparation method is: the first step: the five kind constituent element powder of oxide compound in mutually take by weighing by above-mentioned weight ratio and mixing after, through 950 ℃ with 5 hours calcining after, put into vertical stirring high energy nanometer grinding machine and carry out high-energy ball milling.Ball material weight ratio is not less than 5, and abrading-ball is by diameter 20mm, 16mm and 12mm and footpath 8mm, and 6mm, the sintered carbide ball of 4mm is formed, and the rotating speed that stirs mill is not less than 100 rev/mins.Behind the ball milling 20 hours, take out nanometer/accurate nanopowder, encapsulate stand-by.Fig. 3 is the scanning electron microscope picture of high-energy ball milling institute output nanometer powder.
Second step: with above-mentioned seven kinds of micron-sized metal powder materials, take by weighing by above-mentioned weight percent, mix, and by above-mentioned metallographic phase and oxide compound mutually weight ratio and the first step in nanometer/accurate nanometer powder of being obtained be mixed, adding material again weighs 20% industrial spirit and makes dispersion agent, and add material and weigh 0.5% oleic acid and make properties-correcting agent, adding material weighs 5% polyoxyethylene glycol and makes binding agent, above-mentioned material, properties-correcting agent, binding agent and dispersion agent together add behind the mixing and grind in the general milling machine after 12 hours, take out material, place the temperature-controlled drying case 80 ℃ dry 6～8 hours down.
The 3rd step: the dried material that is obtained in second step, in the rubber model of packing into, hydrostatic pressing under 250MPa, pressurize 10 minutes.
The 4th step: the sample behind the hydrostatic pressing, in baking oven,, enter in the vacuum sintering furnace through after 100-120 ℃ the oven dry, carry out 1250 ℃ of vacuum sintering, sintering temperatures, 90 minutes high temperature hold-times.Below the insulation back furnace cooling to 200 ℃, can from stove, take out, after the anode of making processes screw thread through the car bits, link to each other with the conduction board that confluxes.
The 5th step: carry out the molten-salt electrolytic aluminum test, electrolytic trial carries out in the experimental cell shown in the accompanying drawing 5, and the electrolyzer of Fig. 5 is put in the crucible furnace of external heating type, molten electrolyte is provided and is kept the required temperature of electrolysis by crucible furnace.Mol ratio in the ionogen is
The weight percent of all the other compositions is; Al
2O
3=4%, CaF=3%, NaCl=10%, Na
3AlF
6Be surplus.This ionogen is middle temperature ionogen, and electrolysis is carried out under 850 ℃, interpole gap 4cm, bath voltage 4.5～5.0 shapes.In the electrolytic process, need to calculate Al according to the strength of current of electrolyzer and the electrochemical equivalent of aluminium
2O
3The unit time consumption, regularly add Al
2O
3
Through 30 hours electrolytic trial, electric current and bath voltage were all more stable, and in the electrit of institute's output, the weight percentage of impurity is Fe=0.5%, Si=0.52%, and Cu=0.06%, Ni=0.15% meets the requirement of No. 3 aluminium GBs.In electrolytic process, anodic electroconductibility is good, and erosion resistance is more excellent, after electrolysis finishes, and the weightening finish of anode weight, only at ionogen and atmospheric hand-deliver Jie place that contacts, anode slightly radially reduces, and reducing speed is 25mm/, all the other positions, anode diameter no change.
Embodiment 2: the weight percent of inert anode ceramic phase consists of (%): Al
2O
3: ZrO
2: V
2O
5: CeO
2: MgO=71: 15: 6: 5: 3.Metallographic phase is by Fe, Cu, and Ni, Co, Zn, Ti, Y etc. seven are elementary composition, and the weight percent of each element is in the metallographic phase: Fe: Cu: Ni: Co: Zn: Ti: Y=55: 15: 10: 5: 7: 5: 3.Each oxide components and metal ingredient all provide with the micropowder powder.The weight percent of metal and oxide compound is: the ∑ metal: ∑ oxide compound=25: 75.
Preparation anodic five steps are substantially with embodiment 1, and different with embodiment 1 have following 3 points: the firstth, and before the high-energy ball milling, the oxide compound compound is through 900 ℃ of calcinings with 6 hours; The secondth, when the manufacturing process flow by Fig. 2 carries out conventional ball milling, to add binding agent be polyvinyl acetate, add-on is 7% of a material gross weight; Thirdly not being both when the blank that is pressed into shape is carried out high temperature sintering, is not sintering under vacuum atmosphere.But in purity sintering under 99.9% the argon shield.Sintering temperature is 1450 ℃, sintering time 120 minutes, and all the other operating procedures are with embodiment 1.
The inert anode of producing carries out the electrolysis of aluminum test, and used electrolyzer is with embodiment 1, and used electrolysis process is identical with present domestic Aluminium Electrolysis, and promptly electrolytical mol ratio is
The weight percent of other compositions of ionogen consists of: Al
2O
3=3～5%, CaF=5%, AlF
3=4.5%, surplus is Na
3AlF
6, electrolysis is carried out under 970 ℃ temperature, interpole gap 4.5cm, and 4.5～5.0 volts of bath voltages, electrolytic other operating procedures are with embodiment 1.
Through 50 hours electrolysis, bath voltage and electric current were all more stable, and the impure weight percentage of the electrit of institute's output is Fe=0.75%, Si=0.54%, and Cu=0.04%, Ni=0.14% meets the requirement of No. 3 aluminium GBs.In the electrolytic process, anodic electroconductibility and erosion resistance are all more excellent, after electrolysis finishes, and the anode weightening finish, only at the friendship interface place of ionogen and air, radial dimension slightly subtracts, and reducing speed is 22mm/, all the other positions of anodic, size no change.
Embodiment 3: the weight percent of each composition consists of in the inert anode ceramic phase: AlO
3: ZrO
2: V
2O
5: CeO
2: MgO=81: 10: 4: 3.5: 1.5.Metallographic phase with oxide compound weight ratio mutually is: ∑ metal: ∑ oxide compound=37.5: 62.5.Metallographic phase is by Cu, Fe, and Ni, Cr, Nb, V, Mn etc. seven are elementary composition, and the weight percent of each element consists of in the metallographic phase: Cu: Fe: Ni: Cr: Mn: V: Nb=40: 30: 10: 10: 5: 3: 2.Five operation stepss of preparation anodic are with 1 difference of embodiment substantially with embodiment 1: before (1) high-energy ball milling, oxide compound is through 1000 ℃ of calcinings that keep 4 hours; (2) when carrying out conventional ball milling by the technical process of Fig. 2, used dispersion agent is a water, and used binding agent is a carboxymethyl cellulose, and the add-on of binding agent is 3% of a material gross weight; (3) when the blank that is pressed into shape is carried out sintering, not, but be 99.9% nitrogen protection atmosphere in purity at vacuum atmosphere.1350 ℃ of sintering temperatures, sintering time 150 minutes.All the other operation stepss of preparation anodic are with embodiment 1.
The inert anode of making, electricity carries out electrolysis of aluminum in electrolyzer shown in Figure 5, and used ionogen is with embodiment 2, but different is electrolytical mol ratio with embodiment 2
Electrolysis is carried out under 970-960 ℃ temperature, interpole gap 4cm, and bath voltage 4.5-5.0 volt, all the other are operated with embodiment 2.
Through 30 hours electrolytic trial, the impurity weight percentage of institute's output electrolytic aluminum was: Fe=0.62%:Si=0.50%, and Cu=0.054%, Ni=0.16% meets the requirement of No. 3 aluminium GBs.
In electrolytic process, anodic electroconductibility and erosion resistance are all more excellent, the resistance of electrode does not have in electrolytic process obviously to be increased, bath voltage and electric current are all more stable, and after electrolysis finished, anode weight increased to some extent, but on ionogen and atmospheric friendship Jie line, the anodic radial dimension slightly reduces, and reducing speed is 23.5mm/, all the other position no changes of anodic.
Claims (3)
1. molten-salt electrolytic aluminum inert anode, it is characterized in that: this molten-salt electrolytic aluminum inert anode is by metallographic phase and oxide compound phase composite, and the biphase weight ratio is: metallographic phase: oxide compound phase=25～50: 75～50, oxide compound is by Al
2O
3, ZrO
2, V
2O
5, CeO
2Form with five kinds of constituent elements of MgO, the weight ratio of five kinds of constituent elements is: Al
2O
3: ZrO
2: V
2O
5: CeO
2: MgO=(90～71): (5～15): (2～6): (2～5): (1～3), the oxide compound that is added are commercially pure micropowder powder; The metallographic phase of inert anode is made up of 5 to 7 kinds of metallic elements, and these 5 to 7 kinds of metals are chosen from following 13 kinds of metallic elements: Cu, Ni, Co, Fe, Al, Mn, Zn, Cr, Ti, Nb, V, Ta, and Y, the metal ingredient that is added are the micron powder shape of 99.0～99.9% technical purity;
The preparation method of above-mentioned molten-salt electrolytic aluminum inert anode comprises two stages, and is specific as follows:
One stage is for producing mixed oxide nanoparticle and accurate nanometer powder: take by weighing various oxide compound coarse meals by weight percentage, use mechanical or manual mixing, at 900-1000 ℃ of temperature lower calcination 4-6 hour, put into the ball milling that high energy ball mill carries out 20-26 hour; High energy ball mill is vertical or horizontal stirring mill, and the processing parameter of high-energy ball milling is: ball material weight ratio is no less than 6, and mixing speed is no less than 100 rev/mins; The ball material is 4,6,8,16 by diameter, and other Wimet abrading-ball of five kinds of levels of 25mm is formed; Through the mixed powder of high-energy ball milling, its granularity is 80～200nm;
Two-stage is the preparation inert anode, is undertaken by following five steps:
A. the general milling legal system is equipped with mixed powder: mixed oxide nanoparticle/accurate nanometer powder and mixed metal powder and dispersion agent, binding agent and surface-modifying agent with predetermined weight, together add in the ball mill, and be no less than 8 hours ball milling; Surface-modifying agent is with primary alconol HO-R or oleic acid, add-on be compound heavy 0.5～1.0%; Dispersion agent is industrial spirit or distilled water or pure water; Binding agent is a polyvinyl alcohol, or polyethylene polymer, or polyoxyethylene glycol, or polycarbonate, or polyvinyl acetate, or carboxymethyl cellulose, the add-on of binding agent is that metal mixes 3～7% of grain weight with oxide compound, and binding agent added in the general milling discharging in preceding two hours;
B. cryodrying: the temperature of cryodrying is 80～120 ℃, and the exsiccant time is then according to what of inventory, and the thickness of the bed of material and deciding is generally at 6-8 hour;
C. molded: molded or use rubber mold hydrostatic pressing, forming pressure be 150～250Mpa with metal pattern machinery, different according to inert anode shape and dimensional requirement are pressed into the geometrical shape of the mold shape of shape for routine;
D. the sintering of blank is shaped: blank is sintering in vacuum sintering furnace or protective atmosphere high temperature sintering furnace, 99.99% argon shield of protective atmosphere sintering purity; Vacuum sintering is 10
-1～10
-2Sintering under the vacuum tightness of Pa; Sintering temperature is 1250-1450 ℃, and 90-150 minute sintering high temperature hold-time, the length or the radial shrinkage ratio of column sample are 74～76% before and after the sintering;
E. inert anode is lathed and process screw thread, so that link to each other with the electrolytic conduction board that confluxes.
2. the preparation method of the described molten-salt electrolytic aluminum inert anode of claim 1 is characterized in that its this preparation method's operation is divided into two stages, and is specific as follows:
One stage is for producing mixed oxide nanoparticle and accurate nanometer powder: take by weighing various oxide compound coarse meals by weight percentage, use mechanical or manual mixing, at 900-1000 ℃ of temperature lower calcination 4-6 hour, put into the ball milling that high energy ball mill carries out 20-26 hour; High energy ball mill is vertical or horizontal stirring mill, and the processing parameter of high-energy ball milling is: ball material weight ratio is no less than 6, and mixing speed is no less than 100 rev/mins; The ball material is 4,6,8,16 by diameter, and other Wimet abrading-ball of five kinds of levels of 25mm is formed; Through the mixed powder of high-energy ball milling, its granularity is 80～200nm;
Two-stage is the preparation inert anode, is undertaken by following five steps:
A. the general milling legal system is equipped with mixed powder: mixed oxide nanoparticle/accurate nanometer powder and mixed metal powder and dispersion agent, binding agent and surface-modifying agent with predetermined weight, together add in the ball mill, and be no less than 8 hours ball milling; Surface-modifying agent is with primary alconol HO-R or oleic acid, add-on be compound heavy 0.5～1.0%; Dispersion agent is industrial spirit or distilled water or pure water; Binding agent is a polyvinyl alcohol, or polyethylene polymer, or polyoxyethylene glycol, or polycarbonate, or polyvinyl acetate, or carboxymethyl cellulose, the add-on of binding agent is that metal mixes 3～7% of grain weight with oxide compound, and binding agent added in the general milling discharging in preceding two hours;
B. cryodrying: the temperature of cryodrying is 80～120 ℃, and the exsiccant time is then according to what of inventory, and the thickness of the bed of material and deciding is generally at 6-8 hour;
C. molded: molded or use rubber mold hydrostatic pressing, forming pressure be 150～250Mpa with metal pattern machinery, different according to inert anode shape and dimensional requirement are pressed into the geometrical shape of the mold shape of shape for routine;
D. the sintering of blank is shaped: blank is sintering in vacuum sintering furnace or protective atmosphere high temperature sintering furnace, 99.99% argon shield of protective atmosphere sintering purity; Vacuum sintering is 10
-1～10
-2Sintering under the vacuum tightness of Pa; Sintering temperature is 1250-1450 ℃, and 90-150 minute sintering high temperature hold-time, the length or the radial shrinkage ratio of column sample are 74～76% before and after the sintering;
E. inert anode is lathed and process screw thread, so that link to each other with the electrolytic conduction board that confluxes.
3. the application of the described molten-salt electrolytic aluminum inert anode of claim 1 is characterized in that the surrogate of this inert anode as the molten-salt electrolytic aluminum carbon annode.
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| CN101717969A (en) * | 2009-12-18 | 2010-06-02 | 中国铝业股份有限公司 | Alloy material suitable for inert anode of metal fused-salt electrolysis cell |
| CN104005054A (en) * | 2013-02-22 | 2014-08-27 | 王宇栋 | Metal oxide ceramic inert anode and preparation method and application thereof |
| RU2537622C1 (en) * | 2013-06-21 | 2015-01-10 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Composition of charge for manufacture of oxide-metal inert anode |
| CN103556184B (en) * | 2013-11-13 | 2016-01-20 | 昆明冶金研究院 | A kind of full moist type nano-Ni/Fe 2o 4the preparation method of-NiO-Cu-Ni cermet inert anode |
| CN107260005A (en) * | 2017-08-09 | 2017-10-20 | 泾县信达工贸有限公司 | A kind of resistant electric cooker lid |
| CN109336046B (en) * | 2018-11-20 | 2020-07-31 | 太原科技大学 | Preparation process of PEG-based composite solid polymer electrolyte applied to anodic bonding |
| CN113249755B (en) * | 2021-05-12 | 2023-05-02 | 郑州大学 | Inert anode material and preparation method and application thereof |
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