Fe-30Ni-5NiO alloy as inert anode for low-temperature aluminum electrolysis

Fe-30Ni-5NiO alloy anodes were prepared by a spark plasma sintering process for aluminum electrolysis. NiO nano-particles with the size of ∼20 nm were dispersed in the anodes. The oxidation behaviors of the anodes were investigated at 800°C and 850°C, respectively. The electrolysis corrosion behaviors were tested in a cryolite-alumina electrolyte at a low temperature of 800°C with anodic current densities of ∼0.5 A/cm². The results indicated that the oxidation kinetic of the anodes followed a parabolic law. A continuous Fe₂O₃ film selectively formed on the surface of the anode during the electrolysis process. A semi-continuous Al₂O₃ layer was observed at oxide film/alloy interface, probably caused by an in-situ chemical dissolution process.     

新型炼铝电极材料

研制了一种新型铝电解金属陶瓷惰性阳极,阳极基体由Fe-Ni-Co-Al-O构成.在电解温度960℃,氧化铝质量浓度为6.0%,阳极电流密度为1.0 A/cm2,分子比为2.6的电解质中对其进行了10 h的电解.电解过程平稳,电解铝产品纯度达到96%～99%,阳极气体中氧气的含量为98%,反电动势为2.45 V,高于理论值0.25～0.35 V.此阳极具备较好的导电性、抗氧化和耐腐蚀性.采用X射线衍射和电子探针微分析仪(EPMA)对电解后的阳极进行分析,发现阳极表面存在铁酸镍、铝酸铁等尖晶石型化合物,阳极表面下层为铝酸铁、钴酸镍等陶瓷相以及金属相;金属相和陶瓷相相互弥散分布构成结构致密的金属陶瓷层.     

铝电解惰性阳极研究现状

惰性阳极是铝工业新技术的一个重要课题,本文对近年来铝电解阳极材料多已集中在金属、金属陶瓷、氧化物陶瓷和氧化铈涂层几个方面的现状及研究进展分别加以介绍。指出铝电解惰性阳极的研制一开始就遇到的问题,如氧化,腐蚀,产出铝受惰性阳极材料的污染,阳极寿命,导电性和成本问题仍未完全解决。     

铝电解用改性预焙碳阳极实验室研究

为了制备能应用于工业生产节能降耗和增效的改性预焙碳阳极，首先在实验室进行了阳极添加剂组分的选择优化及复合添加剂的合成，筛选出了含有A1，Mg，F，O等多种元素的复合添加剂，制备出含有该类复合添加剂的AB类改性预焙碳阳极，并对其进行了物理化学性能和电化学性能的测试。实验室研究表明，与对比(空白)阳极相比，含有AB类添加剂的改性预焙碳阳极具有理想的节(电)能和节(碳)耗效果。重点阐述了AB类改性预焙碳阳极的各项性能。     

Preparation and preliminary testing of cermet inert anode for aluminum electrolysis

1　INTRODUCTIONAluminumhasthelargest productivityamongthenonferrousmetals ,2 4Mtperyearintheworld .Whilegreatprogresshavebeenmadeintheprimaryaluminum production ,theindustrycontinuestopur sueresearchtosolvesomeformidablechallenges ,suchas quitealargeenergyintensity(14 0 0 0 15 0 0 0kW·hpertonaluminum) ,highcon sumptionofcarbonanode(5 0 0 6 0 0kgpertonalu minum) ,significantemissionsofgreenhousegas(1.71tpertonaluminum )andotherdetrimentalgases ,highcapitalinvestmentandcost[1] .Inertelectr…     

The economics of inert anodes and wettable cathodes for aluminum reduction cells

Estimating the impact of inert-anode and wettable-cathode technologies on smelter costs must be speculative because no such technologies have yet been commercialized. Even so, some broad conclusions can be drawn about the economic merit of inert anodes in retrofit and greenfield smelter scenarios. Study suggests that retrofitting inert anodes to existing prebake cells generates insufficient economic benefit to justify this objective. Drained cathode cells offer potential for energy savings coupled with increased production, provided that the cell life is greater than three years. Unlocking the potential value of both inert anode and wettable cathode materials will require their use in vertical electrode configurations, where the impact on operating costs and, particularly, capital costs, is expected to be significant. To be economically and technically viable, vertical electrode cells will require wear rates of less than approximately 5 mm per year on the inert electrode surfaces, much less than has so far been reported. For more information, contact Jeff Keniry, Alumination Consulting Pty. Ltd., 2 Governors Drive, Mt. Macedon, VIC 3441, Australia; +61-3-5426-4124; fax +61-3-5426-4248; e-mail jkeniry@netcon.net.au.     

Corrosion behavior of Cu-Ni-Ag-Al alloy anodes in aluminium electrolysis

The behavior of Cu-Ni-Ag-Al alloy used as anode for aluminum electrolysis was directly visualized in a two-compartment see-through cell during electrolysis, and its performances were tested at 850℃ in acidic electrolyte molten salts consisting of 39.3%NaF-43.7%AlF3-8%NaCl-5?F2-4%Al2O3 for 40 h in a laboratory cell. The results show that nascent oxygen oxidizes the anodic surface to form oxide film at the beginning of electrolysis. X-ray diffraction analysis of alloy surface show that the oxide film on the anodic surface consists of CuO, NiO, Al2O3,CuAl2O4 and NiAl2O4. However, SEM image shows the oxide film is porous, loose and easy to fall into electrolyte and to contaminate aluminum. The corrosion mechanism of metal anodes was analyzed.     

添加剂BaO对铝电解用xCu/（10NiO-NiFe_2O_4）金属陶瓷惰性阳极腐蚀性能的影响

制备铝电解用xCu/（10NiO-NiFe2O4）和1BaO-xCu/（10NiO-NiFe2O4）（x=5,10,17）金属陶瓷惰性阳极,在传统电解质中以电流密度1.0A/cm2进行实验室电解腐蚀实验。结果表明：金属Cu被腐蚀,在阳极表面留下了许多孔洞从而导致在电解过程中电解质向阳极内部渗透;金属陶瓷5Cu/（10NiO-NiFe2O4）,10Cu/（10NiO-NiFe2O4）,17Cu/（10NiO-NiFe2O4）,1BaO-5Cu/（10NiO-NiFe2O4）,1BaO-10Cu/（10NiO-NiFe2O4）和1BaO-17Cu/（10NiO-NiFe2O4）的腐蚀速率分别为2.15,6.50,8.30,4.88,4.70和4.48cm/a;添加剂BaO对10Cu/（10NiO-NiFe2O4）和17Cu/（10NiO-NiFe2O4）金属陶瓷的抗腐蚀性能是有利的,因为添加剂BaO能有效提高其致密度从而提高其抗腐蚀性能;但BaO对5Cu/（10NiO-NiFe2O4）金属陶瓷的抗腐蚀性能是不利的,可能是因为聚集在晶界的添加剂BaO加速了金属陶瓷的腐蚀。     

铝电解用NiFe2O4-10NiO基金属陶瓷惰性阳极的耐腐蚀性能

制备铝电解用NiFe2O4-10NiO基金属陶瓷惰性阳极,并在实验室电解槽中考察其电解腐蚀性能。结果表明,电解过程中虽然惰性阳极在960°C熔盐电解质中表现出优异的耐腐蚀性能,但采用XRD、SEM/EDX和金相分析其物相组成和微观结构后发现,电解后阳极中的金属相发生了优先腐蚀,在阳极表面产生大量孔洞。NiFe2O4相中的 Fe 元素的优先溶解可能导致 NiFe2O4晶粒的不均匀腐蚀。溶解在电解液中的 Al2O3与阳极中的 NiO 或FeO 发生反应生成的 NiFe2O4-NiAl2O4-FeAl2O4相对 NiO 相的吞并以及体积膨胀,阳极表面形成致密的NiFe2O4-NiAl2O4-FeAl2O4保护层。因此,致密的NiFe2O4-NiAl2O4-FeAl2O4保护层可以阻挡阳极表面金属相的损失和陶瓷相的腐蚀。     

Industrial preparation and performance testing of property-modified prebaked carbon anodes for aluminum electrolysis

1　ＩＮＴＲＯＤＵＣＴＩＯＮＩｔｉｓｗｅｌｌｋｎｏｗｎｔｈａｔａｌｕｍｉｎｕｍｅｌｅｃｔｒｏｌｙｓｉｓｉｓａ“ｌａｒｇｅｆａｍｉｌｙ”ｏｆｅｌｅｃｔｒｏｅｎｅｒｇｙｃｏｎｓｕｍｐｔｉｏｎ .Ｉｎｔｈｅｍｅａｎｔｉｍｅ ,ｃａｒｂｏｎａｎｏｄｅｓａｒｅｕｓｅｄｕｐｃｏｎｔｉｎｕｏｕｓｌｙｉｎｔｈｅｐｒｏｃｅｓｓｏｆｅｌｅｃｔｒｏｌｙｓｉｓ ,ｓｏｔｈｅａｌｕｍｉｎｕｍｅｌｅｃｔｒｏｌｙｓｉｓｉｓａｌ ｓｏｃａｌｌｅｄ“ｌａｒｇｅｆａｍｉｌｙ”ｏｆｃａｒｂｏｎｃｏｎｓｕｍｐｔｉｏｎ .Ｆｏｒａｌｏｎｇｔｉｍｅ…     

电解质对铝电解用阳极润湿性的研究

测试了熔融状态下三种不同组分的电解质对碳阳极和自制的镍铁尖晶石基金属陶瓷惰性阳极的润湿性.实验结果表明,电解质对惰性阳极的润湿性明显好于对碳阳极的润湿性,不同电解质成分对阳极的润湿角有一定影响.工业冰晶石中加入Al2O3能够改善电解质对阳极的润湿性,添加剂CaF2对提高电解质对惰性阳极的润湿性基本没有贡献.     

铝电解金属陶瓷惰性阳极的机械加工及大型化研究

本文用普通钻头和设计的专用走具,采用传统机械加工方法对金属陶瓷铝电解惰性阳极钻孔,同时也研究了金属陶瓷惰性阳极的磨削、抛光等加工方法。用这些方法成功地解决了金属陶瓷铝电解惰性阳极的机械加工和大型化问题。     

小型金属陶瓷惰性阳极的低温铝电解实验

本实验采用自行研制的小型镍铁尖晶石基惰性阳极 (直径 43mm)与冰晶石 -氧化铝系低温电解质 ,在 85 0℃下进行电解实验 ,保持阳极电流密度lA/cm2 ,实验共进行 11小时 ,得到了少量的金属铝。实验结果表明 ,在此电解温度下 ,构成惰性阳极的金属陶瓷材料抗电解质腐蚀的能力较强 ;阳极在实验后出现的裂纹说明材料的抗热震性有待进一步提高 ,而且本实验中惰性阳极与金属导杆的连接方式也需更深入研究。     

铝电解用NiFe2O4-Cu金属陶瓷惰性阳极的制备

以高温固相合成法合成的NiFe2O4陶瓷粉体和金属Cu粉为原料, 采用冷压-烧结法制备了Cu含量在5%～20%之间的NiFe2O4-Cu金属陶瓷惰性阳极, 研究了烧结气氛和烧结温度对其物相组成、微观形貌和基本物理性能的影响. 结果表明 通过控制烧结气氛中氧分压在NiO和Cu2O的离解反应平衡氧分压之间, 可以制备出具有目标物相组成的NiFe2O4-Cu金属陶瓷; 烧结温度和保温时间对所得NiFe2O4-Cu金属陶瓷的相对密度有较大影响; NiFe2O4和Cu之间的不润湿性限制了NiFe2O4-Cu金属陶瓷烧结温度的提高和保温时间的延长, 在保证金属相分布均匀且不溢出的前提下, 所制备的NiFe2O4-Cu金属陶瓷的相对密度较小; 金属相Cu含量越高, NiFe2O4-Cu金属陶瓷最高烧结温度越低、最长保温时间越短, 从而相对密度越低、孔隙率越高; 除了尽量降低金属相含量外, 还可向NiFe2O4-Cu金属陶瓷中添加其他金属如Ni和Co等, 以改善陶瓷相与金属相之间的润湿性, 以提高烧结温度, 进而提高其相对密度和耐腐蚀性能.     

Structure and high-temperature oxidation behaviour of Cu-Ni-Fe alloys prepared by high-energy ball milling for application as inert anodes in aluminium electrolysis

Cu_xNi_85−xFe₁₅ (0 ? x ? 85 wt.%) compounds were prepared by mechanical alloying. Monophased face centered cubic (fcc) Cu-Ni-Fe alloys were obtained after 10 h of milling for x varying from 0 to 50, whereas bi-phased compounds fcc Cu-Ni-Fe + body centered cubic (bcc) Fe were formed with richer-Cu compounds. Their oxidation kinetics in air at 750 °C is parabolic for all compositions and increases drastically for x > ∼30. A stable anode for aluminium electrolysis in low-temperature (700 °C) KF-AlF₃ electrolyte was obtained for 65 ? x ? 85. However, a substantial increase of the Cu contamination in produced aluminium was observed for x > 70.     

NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>-based cermet inert anodes for aluminum electrolysis

Recent developments in the preparation, sintering process, mechanical properties, and thermal shock resistance of cermet inert anodes for aluminum electrolysis are reviewed in this paper. To obtain the desired technologies of low-temperature activated sintering of cermet inert anodes, the effects of material composition, sintering atmosphere, sintering temperature, and sintering aids on the densifi cation and microstructure of NiFe₂O₄-10NiO- based ceramics and cermets were studied. To obtain the toughening and strengthening technology of the cermet, the effects of material composition including ceramic and metallic phases are discussed. The cermet inert anodes with high density and mechanical properties were prepared through adjustment of material composition and sintering technology and selection of feasible sintering aids.     

电解生产铝钛合金研究与实践

介绍了在铝电解槽中加入含钛氧化钛直接电解生产铝钍合金的工业实践，通过调整电解工艺技术条件．使电解生产过程受到的影响降到最低程度，电解生产的铝钛合金应用于内燃机活塞与汽车轮毂,完全满足活塞与轮艇机械性能的要求。同时大幅度降低了铝钛合金制造成本。经济效益显著。并具有推广价值。     

电解法制取铝锶合金的研究

本文研究了电解质组成、电解温度、阴极电流密度、电解时间等因素对电解法生产铝－锶合金工艺的影响。在此实验基础上,确定了电解法生产铝－锶合金的可行性工艺条件。     

Preliminary testing of NiFe_2O_4-NiO as ceramic matrix of cermet inert anode in aluminum electrolysis

1　INTRODUCTIONTheideaofusinginertanodes(alsocallednon consumableoroxygen evolvinganodes)inaluminumproductionisasoldastheHall H啨ｒｏｕｌｔｐｒｏｃｅｓｓ ,dat ingbacktothediscoveryofoneoftheinventors ,Hall[1] .Inertanodesareintendedtoreplacethecon sumablecarbonanodethatiscurrentlyused .Withacarbonanode ,thecellreactionisAl2 O3+ 3/ 2C =2Al+ 3/ 2CO2 (1)where　acryolite basedmelt(Na3AlF6 AlF3 CaF2 )atnear 96 0℃servesassolventforthealumina .Withaninertanode ,thecellreactionwillbeAl2 …     

Influence of the iron content in Cu–Ni based inert anodes on their corrosion resistance for aluminium electrolysis

Mechanically alloyed (Cu_3.25Ni)_100−xFe_x materials (x = 0, 15 and 30 wt.%) were evaluated as inert anodes for aluminium electrolysis in KF–AlF₃ (700 °C) electrolyte. For x = 0, the cell voltage was unstable and high (5–6 V) due to the formation of an insulting NiF_x layer at the metal–oxide interface. For x = 15 and 30, the formation of a Cu₂O-rich external scale with a protective NiFe₂O₄-rich intermediate layer was favoured, resulting in a lower (∼4 V) and more stable cell voltage. The purity of the produced Al was 98.96, 99.31 and 99.20 wt.% for x = 0, 15 and 30, respectively.