Alumina solubility in molten salt systems of interest for aluminum electrolysis and related phase diagram data

The solubility of alumina in molten Na₃AlF₆ containing various amounts of AlF₃, CaF₂, and LiF was determined by measuring the weight loss of a rotating sintered corundum disc. The results were fitted to the following empirical expression: 1 $$ [Al_2 O_3 ]_{sat} = A\left( {\frac{t} {{1000}}} \right)^B $$ where 2 $$ \begin{gathered} A = 11.9 - 0.062[AlF_3 ] - 0.003[AlF_3 ]^2 - 0.50[LiF] \hfill \\ - 0.20[CaF_2 ] - 0.30[MgF_2 ] + \frac{{42[LiF] \cdot [AlF_3 ]}} {{2000 + [LiF] \cdot [AlF_3 ]}} \hfill \\ B = 4.8 - 0.048[AlF_3 ] + \frac{{2.2[LiF]^{1.5} }} {{10 + [LiF] + 0.001[AlF_3 ]^3 }} \hfill \\ \end{gathered} $$ where the square brackets denote weight percent of components in the system Na₃AlF₆-Al₂O₃ (sat)-AlF₃-CaF₂-MgF₂-LiF and t is the temperature in degree Celsius. The standard deviation between the equation and the experimental points in the temperature range from 1050 °C to about 850 °C was found to be 0.29 wt pct Al₂O₃. A series of revised phase diagram data of interest for aluminum electrolysis was derived based on the present work and recently published data for primary crystallization of Na₃AlF₆ in the same systems.     

物理富集—熔盐电解法从二次铝灰回收金属铝

二次铝灰是铝工业生产过程中产生的固体废弃物,含有金属铝、氧化铝和氮化铝等。通过球磨—筛分富集铝灰中的金属铝,研究球磨过程铝灰的粒度分布和金属铝的分离规律。结果表明,球磨后铝灰中的金属铝粒径变大,而其他盐类组分变细。较优条件是球磨3 h并筛分,粒度范围97～150μm的铝灰中金属铝的质量分数为24.51%,金属铝的质量占原料中金属铝总质量的41.40%。在冰晶石熔盐中电解最优条件下球磨—筛分后的铝灰,XRF分析表明：电解产物中Al和Si的质量分数分别为97.3%和1.6%,铝回收率为45.89%,电流效率为46.06%。     

Liquidus temperatures in calcium ferrite slags in equilibrium with molten copper

Experimental laboratory methods have been developed that enable phase-equilibria studies to be carried out on slags in the system Ca-Cu-Fe-O in equilibrium with metallic copper. These techniques involve equilibration at temperature, rapid quenching, and chemical analysis of the phases using electron-probe X-ray microanalysis (EPMA). Equilibration experiments have been carried out in the temperature range of 1150 °C to 1250 °C (1423 to 1523 K) and in the composition range of 4 to 80 wt pct “Cu₂O,” 0 to 25 wt pct CaO, and 20 to 75 wt pct “Fe₂O₃” in equilibrium with metallic copper. Liquidus and solidus data are reported for the primary-phase fields of spinel (magnetite) and dicalcium ferrite. The resulting data have been used to construct liquidus isotherms of the CaO-“Cu₂O”-“Fe₂O₃” system at metallic copper saturation.     

流水线镁电解熔盐体系密度的研究

利用阿基米德方法研究流水线镁电解熔盐体系密度, 旨在确定适合于流水线镁电解熔盐的较优控制参数, 为生产提供指导, 为同行提供理论参考.研究结果表明:在MgCl₂-KCl-NaCl熔盐体系中, 随着氯化镁的浓度增加, 熔盐的密度增大; 随着氯化钾浓度的增加, 熔盐的密度减小; 随着氯化钠浓度的增加, 高钾含量的熔盐密度增大, 高镁含量的熔盐密度减小.当体系中出现KMgCl₃时, 熔盐的密度急剧增大; 当体系中出现K₂MgCl₄时, 熔盐的密度急剧减小.在生产中, 熔盐组分较优控制范围为: W_KCl: 50 %~70 %, W_NaCl: 18 %~23 %, W_MgCl2: 12 %~18 %; 熔盐温度较优控制范围为: 680~700 ℃.      

Electrodeposition of magnesium-yttrium alloys by molten salt electrolysis

Electrodeposition of magnesium-yttrium alloys from molten salts was studied by electrochemical techniques.LiF-YF3 was electrolyte system with magnesium oxide and Yttrium oxide as raw materials.It was proved that Mg2+ and Y3+was deposited more prior than other ions during cyclic voltammetry and potential step measurement at 1050 °C.Voltammograms showed Mg2+ could be deposited at-0.5 V,and Y3+ could be deposited at-0.7 V on tungsten electrode compared with platinum electrode.The sedimentation of Mg2+ was more positive about 230 mV than that of other ions in electrolyte.The electrolytic codeposition of yttrium and magnesium was 0.58 V on condition that the weight ratio of Y2O3/MgO was 4:1.Chronopotentiogram indicated that the process of electrodeposition of magnesium-yttrium alloys on tungsten electrode was controlled by diffusion of ions from electrolyte to electrode interface.It was feasible to prepare Magnesium-Yttrium alloys by controlling content of ions in molten salt electrolyte.     

Electrodeposition of magnesium-yttrium alloys by molten salt electrolysis

Electrodeposition of magnesium-yttrium alloys from molten salts was studied by electrochemical techniques. LiF-YF₃ was electrolyte system with magnesium oxide and Yttrium oxide as raw materials. It was proved that Mg²⁺ and Y³⁺was deposited more prior than other ions during cyclic voltammetry and potential step measurement at 1050 °C. Voltammograms showed Mg²⁺ could be deposited at ?0.5 V, and Y³⁺ could be deposited at ?0.7 V on tungsten electrode compared with platinum electrode. The sedimentation of Mg²⁺ was more positive about 230 mV than that of other ions in electrolyte. The electrolytic codeposition of yttrium and magnesium was 0.58 V on condition that the weight ratio of Y₂O₃/MgO was 4:1. Chronopotentiogram indicated that the process of electrodeposition of magnesium-yttrium alloys on tungsten electrode was controlled by diffusion of ions from electrolyte to electrode interface. It was feasible to prepare Magnesium-Yttrium alloys by controlling content of ions in molten salt electrolyte.     

熔盐电解制备Al-Cu-Y合金电解质 体系黏度的研究

采用旋转法测定了熔盐电解制备Al-Cu-Y合金的电解质体系Na₃AlF₆-AlF₃-LiF-MgF₂-Al₂O₃-CuO-Y₂O₃在温度900~1 000 ℃范围内的黏度,通过分析数据研究温度及Al₂O₃、Y₂O₃、CuO添加量对熔盐黏度的影响,确定了温度、熔盐组分和黏度之间的关系.结果表明:在温度900~1 000 ℃范围内,体系随温度升高,黏度减小;随Al₂O₃、Y₂O₃、CuO的含量增大,黏度增大;在900~1 000 ℃范围体系黏度（η）随温度（T）以及氧化物的含量W_Al2O3、W_Y2O3、W_CuO符合回归方程η=0.075-6.49×10-5T+3.7×10-4W_Al2O3+5.73×10-4W_Y2O3+6.78×10-4W_CuO.      

Dissolution of alumina in molten cryolite

Alumina powder dissolves rapidly in molten cryolite,i.e. in 4 to 8 seconds, provided that the particles are effectively dispersed in the melt. At alumina contents well below saturation the time of dissolution is independent of the alumina concentration, and it is not appreciably affected by additions of NaF, A1F₃, or CaF₂. Coarse grains dissolve more slowly than fine grains and α-Al₂O₃ (floury) dissolves more slowly than γ-Al₂O₃ (sandy). The rate-controlling step appears to be a slow chemical reaction. Bottom sludge in industrial cells contains about 40 pct A1₂O₃. This material has a higher α/γ-ratio than the alumina being fed to the cells, while the grain size is smaller due to disintegration of aggregates. The time of dissolution is identical to that of any other alumina with the same α/γ-ratio.     

Influence of Al2O3 on the reoxidation of aluminum in molten cryolite

The influence of Al₂O₃ content on the reoxidation reaction at 1293 K between CO₂ and Al dissolved in molten cryolite was examined. The rate and extent of the reaction were evaluated as the concentration of Al₂O₃ was varied from 0 to 12 wt pct at 4 pct intervals. The cryolite, under an argon atmosphere, was saturated with Al before CO₂ was introduced. High initial reaction rates were observed with a quasisteady state condition established 30 to 60 min after beginning an experiment. Increasing the Al₂O₃ content of the melt significantly reduced the initial rate, but it was not found to alter the steady rate for a given flow system. This phenomenon was observed for systems where CO₂ was passed over or bubbled through the molten cryolite. Bubbling the CO₂ through the molten cryolite led to increases in both the initial and steady state rates. M. K. Han, formerly a Graduate Fellow with the University of Washington.     

氟化物体系熔盐电解制备YNi合金

以Y2O3为电解原料,以金属镍棒为自耗阴极、石墨板为阳极,在常规的石墨电解槽中采用氟化物体系熔盐电解法制备了YNi合金.研究了电解时间、电解温度、电解质组成、阴极电流密度等主要技术参数对电解过程的影响,并对所制备的钇镍合金进行了表征.结果表明,熔盐电解制备钇镍合金的较优工艺条件为:电解温度1000℃,电解质YF3与Li...     

Solutions of iron oxides in molten cryolite

All the iron oxides (FeO, Fe₃O₄, Fe₂O₃, and FeAl₂O₄) dissolve in cryolite-alumina melts to give solutions containing both Fe(II) and Fe(III). The factor controlling the Fe(II)/Fe(III) ratio is the oxygen pressure, and experimental results are interpreted on that basis. Predictions are made of the variation of solubility with oxygen pressure, and the standard potential of the Fe²⁺/Fe³⁺ redox couple is calculated. The anode and anode gas of an industrial Hall-Heroult cell appear to be insufficiently oxidizing to cause significant conversion of Fe(II) to Fe(III). An anomaly in the liquidus diagrams for FeF₂ – Na₃AlF₆ and FeO – Na₃AlF₆ is accounted for in terms of solid solution of FeF₂ in cryolite. This article is based on a presentation made at “The Milton Blander Symposium on Thermodynamic Predictions and Applications” at the TMS Annual Meeting in San Diego, California, on March 1–2, 1999, under the auspices of the TMS Extraction and Processing Division and the ASM Thermodynamics and Phase Equilibrium Committee.     

熔盐电解法制备铝钙合金中的反电动势

研究了在CaCl2-CaF2纯钙盐体系中下沉式铝液槽结构熔盐电解法生产Al-Ca合金新工艺,采用连续脉冲-示波器法测定电解过程的反电动势,研究了在实验室条件下电解温度、电流密度、电解时问和极距对熔盐电解法制取铝钙合金的反电动势的影响.用熔盐电解法并采用铝阴极生产Al-Ca合金比对掺法更加节省电能,降低了Al-Ca合金的生产成本,是一种有经济价值的生产方法,有很好的发展前景.     

熔盐电解制备钨铜合金粉体槽内温场条件分析

在熔盐电解法由Na2WO4和CuO制取钨铜合金粉体的研究基础上,分析电解槽内的温度场分布,特别是电极区域的温度分布情况对电解行为的影响.通过位移法测量,采取比较法分析实验误差,结果表明:电解过程中2个主要的外部条件,即电解槽内温场分布与电场分布是联动的;温度条件影响着电极电位;同时,外部槽电压通过电流扰动槽内温场,使电极区域温场分布不均.     

熔盐预电解脱水与电解时间对溶盐电解TiO_2脱氧行为的影响

以无水氯化钙作为熔盐,采用熔盐电解法对TiO2阴极片进行脱氧,通过X射线衍射(XRD)和扫描电镜(SEM)对TiO2电解产物的相组成、电极表面形貌与元素组成进行观察与分析,研究熔盐的预电解脱水与熔盐电解时间对TiO2电解脱氧行为的影响。结果表明,熔盐未经预电解时,TiO2阴极片不发生脱氧反应,电解产物只有CaTiO3相;熔盐经预电解脱水后,TiO2电解产物部分或全部为低价钛氧化物,预电解时间达到15h即可有效去除熔盐中的水分,从而获得较佳的熔盐电解脱氧效果,电解产物为氧含量较低的Ti2O。TiO2电解脱氧是分步进行的,随电解进行,先后出现Ti2O3、TiO、Ti2O,由于钛的化合价逐渐降低,所需分解压升高,导致脱氧效率逐渐降低。TiO2阴极的脱氧反应是由表面到心部进行,电解后的阴极片明显分层,表层为氧含量较低的Ti2O,中间层为CaTiO3和钛的低价氧化物,心部为CaTiO3。     

熔盐电解制备铜粉的实验研究

文中研究了在NaCl-KCl-CuO体系中采用熔盐电解法直接制取铜粉的方法.基本反应条件为:电解温度740~820 ℃;槽电流12~15 A;阴极电流密度110~140 mA/cm2;槽电压2.2~3.2 V;电解时间1.5~3.5 h.对阴极电解产物进行了X射线衍射（XRD）及铜粉粒度分析,同时用扫描电镜（SEM）及能谱仪（EDS）对产物的形貌及元素含量进行了分析.结果表明:在上述条件下可以得到铜粉末,产物纯度在98 %以上且平均粒度为0.91 μm.      

NaCl-KCl-Na_2WO_4-CuO体系电解制备钨铜复合粉体研究

文中研究采用熔盐电解以由Na2WO4和CuO为活性物质电解获得钨铜合金复合前驱粉体.通过循环伏安法对电解质体系及电极过程进行定性分析认为Na2WO4减缓体系活性物质扩散速度,CuO与Na2WO4的电解非同步进行.通过改变活性物质的加入方式进行对比实验,结果表明：在温度750℃;以一定比例KCl-NaCl混合熔盐为电解质,在起始槽电压1 V,先加入CuO电解2 h;后加入Na2WO4,调整槽电压至2 V电解3 h,对产物进行X射线衍射（XRD）和扫描电镜（SEM）及能谱分析（EDS）表明,可以获得纯度达到98%的W-Cu合金粉体.     

Interfacial tension of aluminum in cryolite melts

The interfacial tension between aluminum and cryolite melts containing different salt additions has been measured based on a combination of the sessile drop and X-ray radiographie technique. A computer program was used to calculate the interfacial tension from approximately twenty randomly measured coordinate points of the drop profile. Aluminum and salt mixtures containing different amounts of Na₃AlF₆, A1F₃, NaF, A1₂O₃, CaF₂, KF, LiF, and NaCl were melted in a graphite or alumina crucible in a graphite resistor furnace under an argon atmosphere. The interfacial tension was found to be strongly dependent on the NaF/AlF₃ ratio. At the cryolite composition the interfacial tension was 481 mN/m at 1304 K, while it was 650 mN/m when the NaF/AlF₃ ratio was equal to 1.5. The change in interfacial tension with composition is explained by sodium enrichment of the Al/melt interface. Additions of A1₂O₃ increased the interfacial tension for a given NaF/AlF₃ ratio. KF was found to be surface active, while CaF₂, LiF, and NaCl slightly increased the interfacial tension by decreasing the sodium activity.     

铝用石墨质阴极不同焙烧温度下孔隙结构演化

采用图像分析方法研究铝用石墨质阴极在不同焙烧温度下孔隙结构特征及其演变,考察孔隙率、孔径分布、形状因子、视孔隙比表面积、连通性等参数的变化规律和孔隙复杂度的分形特征.结果表明：随着焙烧温度增加,孔隙率逐渐增大,而视孔隙比表面积、形状因子和连通性呈先减小后增大趋势;石墨质阴极试样不同温度下焙烧生成孔隙均符合分形规律,借助图像分析孔隙结构参数和分形维数可界定不同典型焙烧温度下阴极孔隙结构的演变特征,并据此提出相应的孔隙特征演化模式.     

The apparent solubility of aluminum in cryolite melts

The apparent solubility of aluminum in cryolite melts saturated with A1₂O₃ has been determined by titration with electrolytically generated O₂. The results may be expressed by wt pct Al = − 0.2877 + 0.0268 (NaF/AlF₃ wt ratio) + 2.992 × 10⁻⁴ (temp °C) − 0.00192 (% CaF₂) −0.00174 (% Li₃AlF₆) −0.00288 (% NaCl) with a standard deviation of ±0.017. Ranges covered were ratio 0.8 to 2.3, temperatures 969° to 1054°C, CaF₂ ≤ 14 pct, Li₃AlF₆ ≤ 20 pct, and NaCl ≤ 10 pct. There was no significant effect of adding 0 to 38. pct K₃A1F₆ or 0 to 10 pct MgF₂. It was found that solubility was approximately proportional to activity of aluminum when Al-Cu alloys were used. Possible mechanisms of solution are discussed. Monovalent aluminum is ruled out on the basis of the variation of solubility with NaF/AlF₃ ratio and a_Al. The favored, but not proven, mechanism involves formation of both sodium atoms and a colloidal dispersion of aluminum.