摘要
FFC法是一种在氯化钙基熔盐体系中将固态金属氧化物直接电解制备固态金属或合金的方法,具有工艺简单,成本低等优点。如果采用惰性阳极则是一种绿色生产工艺。
FFC法不要求固态金属氧化物溶解到熔盐中,避开了传统以氧化物为原料进行低温熔盐电解氧化物溶解度、溶解速度降低等问题。操作温度范围也可以根据需要,通过调整熔盐组成来控制。该法为低温熔盐电解制备金属提供了新思路。另外,氯化钙基氯化物熔盐的低熔点也为实现低温熔盐电解提供了条件。
本论文以CaCl_2-NaCl熔盐为电解质,石墨为阳极,利用FFC法,施加3.1V恒电位,低温熔盐电解固态Al_2O_3、Al_2O_3-MgO、Dy_2O_3-Fe、Dy_2O_3-Fe_2O_3制备出了Al及Al-Mg、DyFe_2合金。
采用直接阿基米德法、CVCC法结合阻抗测量技术测定了550℃～800℃,含CaCl_2质量百分数为71%～87%的铝电解用熔盐电解质体系密度和电导率。结果发现,在550℃～750℃范围,含CaCl_2质量百分数为71%～87%的CaCl_2-NaCl-Al_2O_3(饱和)熔盐体系的密度随着氯化钙含量的增加而增大,但不是线性关系;氧化铝的溶解降低了熔盐体系的电导率,增加了电导活化能。在550℃～800℃范围,含CaCl_2质量百分数为71%～82%的CaCl_2-NaCl-Al_2O_3(饱和)熔盐体系中组元是离子状态,电导率与温度呈线性关系,氯化钙的增加降低了熔盐体系的电导率和电导活化能。
开发出新型石墨孔腔工作电极。其可靠、有效性通过对NiO和TiO_2两种具有代表性氧化物粉体循环伏安曲线和恒电位电解的检测进行了确认。应用新型石墨孔腔工作电极研究了固态Al_2O_3低温熔盐电解机理及阴极还原过程。研究表明Al_2O_3的还原机理是三价铝→铝一步完成,还原过程是部分氧化铝先电解生成金属铝和氧离子,氧离子和钙离子与未电解的氧化铝反应生成CaAl_2O_4和CaAl_4O_7,CaAl_2O_4和CaAl_4O_7进一步还原生成金属铝、CaAl_4O_7和Ca_3Al_2O_6,CaAl_4O_7进一步还原生成金属铝和Ca_3Al_2O_6,Ca_3Al_2O_6最终被还原成金属铝。
对固体Al_2O_3的烧结、电解工艺进行了研究。确定颗粒粒径φ<38μm,烧结温度1400℃,烧结时间9h为氧化铝阴极片合适的烧结工艺条件;液态铝镁合金为导电体,熔盐温度800℃,烧结氧化铝为阴极,含氯化钙质量百分数82%的熔盐为合适的电解工艺条件。
对Al_2O_3-MgO混合粉烧结片电解制备Al-Mg合金进行了研究。确定烧结温度1300℃,烧结时间8h是合适的阴极片烧结工艺条件;研究发现Al-Mg合金制备的阴极还原过程是部分Al_2O_3先被还原生成铝和中间产物CaAl_2O_4,CaAl_4O_7,中间产物和MgAl_2O_4电解生成金属镁和铝,电解出来的金属镁与金属铝合金化形成Al-Mg合金。
对Fe-Dy_2O_3、Fe_2O_3-Dy_2O_3混合粉烧结片电解制备DyFe_2合金进行了研究。研究发现高的氯化钙含量和电解温度对合金制备有利;Fe-Dy_2O_3阴极片电解的阴极过程是氧化镝先电解出金属镝,金属镝扩散到铁粉中形成合金,合金化的过程是DyFe_5→DyFe_3→DyFe_2;烧结温度800℃,烧结时间4h为Fe_2O_3-Dy_2O_3阴极片的合适制备条件。DyFe_2合金电解制备阴极过程是Fe_2O_3先电解出Fe,DyFeO_3电解出Fe和Dy_2O_3,Dy_2O_3再电解出Dy原子,生成的Fe、Dy原子合金化过程是DyFe_5→DyFe_2。分析了阳极气体产生的顺序是先CO_2后CO。
The method of direct electrochemical reduction solid oxides to prepare solid metals or alloys in molten CaCl_2 base chloride salts is named FFC Cambridge Process, which is simple and low cost, and is a green process using the inert anode.
The problems that include oxide required dissolving into molten salt and oxide's low solubility and low dissolved rate in traditional low temperature molten salt can be avoided through FFC method. It is a new method to apply the FFC for preparing metals or alloys in low temperature molten salts. Addition to, CaCl_2-NaCl has the low melt point and it assures the feasibility of application of FFC in low temperature molten salt.
In the paper, the FFC Cambridge Process method was used to prepare Al and Al-Mg, DyFe_2 in molten CaCl_2-NaCl. A graphite rod was employed as the anode and Al_2O_3, Al_2O_3-MgO, Dy_2O_3-Fe, Dy_2O_3-Fe_2O_3 were served as cathode respectively. The voltage between the cathode and the anode was 3.1 V. Preparation of Al and Al-Mg, DyFe_2 alloys in low temperature molten salt by FFC was studied and Al, Al-Mg, DyFe_2 alloys were obtained.
The electrical conductivity and density of molten salts for Al electrolysis was measured by direct Archimedes method and CVCC technology from 550℃to 800℃respectively. The density of molten CaCl_2-NaCl-Al_2O_3 (w(CaCl_2)= 71%-87% corresponding to NaCl, saturated Al_2O_3) systems was increased with the incressing CaCl_2 content, however, the relation of density and CaCl_2 content was not linear from 550℃to 750℃. The additive Al_2O_3 decreased the electrical conductivity, and increased the activation energy of conductance in CaCl_2-NaCl system. The relation of the electrical conductivity of molten CaCl_2-NaCl-Al_2O_3 (w(CaCl_2)= 71%-82%corresponding to NaCl, saturated Al_2O_3) and temperature was linear from 550℃to 800℃. With the CaCl_2 content incresed, the electrical conductivity of systems was decreased, and the activation energy of conductance was also decreased.
The new graphite cavity working electrode is developed and applied. Dependability and validity of the new graphite cavity working electrode was affirmed through testing cycle voltage curves and constant potential electrolysis of the NiO and TiO_2 typical powders. The electrochemical reduction mechanism of solid Al_2O_3 was obtained by the cycle voltage method with the graphite working electrode and the reduction process were known by the constant potential electrolysis at different times. The reduction mechanism of solid Al_2O_3 was one step from Al~(3+)→Al. The reduction process was as follows. Firstly, Al_2O_3 was partially electrolyzed to form Al and O~(2-), then CaAl_2O_4 and CaAl_4O_7 was formed by the O~(2-) and Ca~(2+) in the molten salts compound with Al_2O_3, CaAl_2O_4 was electrolyze to form Al and CaAl_4O_7, and CaAl_4O_7 was electrolyzed to form Al and Ca_3Al_2O_6, finally the Ca_3Al_2O_6 was electrolyzed to form Al.
To prepare the suitable electrolysis cathode Al_2O_3 pellet, the Al_2O_3 particle size, molding pressure, sinter temperature and sinter time were investigated. The optimal conditions of Al_2O_3 cathode pellet preparation were that the particle size was 38μm, the sinter temperature was 1400℃and the sinter time was 9h. The effect of the different cathode materials, such as the commercial Al_2O_3 powder, the Al_2O_3 sintered pellets, corundum powder, corundum tubes and the sintered Al_2O_3 tubes on the electrolysis were studied by using different conductors including metallic wire, melted Al and Al-Mg alloy. The result showed that the melted Al-Mg alloy as the conductor, the sintered Al_2O_3 rods as cathode, at 800℃and in molten salts with w(CaCl_2)= 82% were optimal electrolysis conditions.
The effects of Al_2O_3-MgO mixture's sinter temperature and time on the electrolysis were investigated. The appropriate sintered conditions were at 1300℃and 8h sinter. The electrochemical reduction process of the cathode were as follows. First, Al_2O_3 was electrolyzed to form Al, CaAl_2O_4 and CaAl_4O_7, then MgAl_2O_4 was electrolyzed to form Al and Mg during the Al-Ca compound oxides were electrolyzed, finally the Mg and Al atoms obtained was alloyed.
The effects of the temperature and CaCl_2 content in molten salt on electrolysis were studied when Fe-Dy_2O_3 was used as the cathode. The result indicated that high electrolysis temperature and high CaCl_2 content was advantage to prepare pure DyFe_2. The electrochemical reduction process of Fe-Dy_2O_3 was that as follows. First Dy_2O_3 was electrolyzed to form Dy, then Dy atoms diffused into Fe body, the formation sequence of alloy was DyFe_5→DyFe_3→DyFe_2. The effects of the sinter temperature and time of Fe_2O_3-Dy_2O_3 mixture on electrolysis were investigated. The appropriate sinter conditions were at 800℃and 4h sinter. The effect of the molten salt temperature and CaCl_2 content on the electrolysis was studied. The result indicated that high electrolysis temperature and high CaCl_2 content was advantage to prepare pure DyFe_2. Temperature was key factor to form DyFe_2. The electrochemical reduction process of Fe_2O_3-Dy_2O_3 were that first Fe_2O_3 was electrolyzed to form Fe, then DyFeO_3 was electrolyzed to form Fe and Dy_2O_3, and Dy_2O_3 was electrolyzed to form Dy, finally Fe and Dy were alloyed to form DyFe_5→DyFe_2. The anode gases were CO_2 and CO.
引文
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