New Concept for Electrplysis of Rare Metals-application of hydrogen gas oxidation as anodic reaction=

以H_2气体氧化为阳极反应，研究了稀有金属的电解法。之所以选择钛作为目标材料，是因为它有更广阔的市场。还尝试了另外两种方法，即从氟氯化物熔体电积Ti和在高温下直接电解Ti锭。研究结果总结如下：(1) Ti金属与K_2TIF_6在LiF-NaF-KF熔体中被电原化。不需要对Ti离子进行部分电化学还原，因此与氯化物熔体相比，该过程简化了。H_2气体在碳气电极上的电化学氧化可作为该工艺的阳极反应。电解稳定，电池电压保持很低，约为2V。然而，沉积Ti的形貌通常为粉末状。用清水冲洗盐是不容易的。(2) Ti金属在NaCl-KCI-NaF-KF熔体中以K_2TIF_6电原化。在适当的条件下，可以将阳极电位控制在较低的范围内，实现稳定的电解。不需要对Ti离子进行部分电化学还原。气体电极就不用了。因此，与氯化物熔体和氟化物熔体相比，采用H_2气体氧化作为阳极反应可以简化反应过程。NaCl-KCl-NaF-KF盐比LiF-NaF-KF盐更容易被水从Ti矿床中去除。(3)在电渣重熔装置中对含TiO_2的CaF_2-CaO混合物施加大直流电流。这种混合物被焦耳热熔化。在电池底部的阴极处获得钛金属。结果表明，该工艺在理论上是可行的，但必须提供足够的热量来实现该工艺。

Electrolysis of rare metal has been studied by using H_2 gas oxidation as anodic reaction. Ti was chosen as a target material because of its wider market. Two other methods were also tried, namely electrowinning of Ti from a fluoride-chloride melt and direct electrolysis of a Ti ingot at high temperature.The results are summaized as follows ;(1) Ti metal was electrowon in a LiF-NaF-KF melt with K_2TIF_6. Partial electrochemical reduction of Ti ions was not necessary so that the process was simplified in comparison to that in a chloride melt. The electrochemical oxidation of H_2 gas at a carbon gas electrode could be used as an anodic reaction for the process. Stable electrolysis was performed, and the cell voltage kept very low as about 2V.However, the morphology of the deposited Ti was usually powdery. Rinsing of the salt with water was not easy.(2) Ti metal was electrowon in a NaCl-KCI-NaF-KF melt with K_2TIF_6. The anode potential could be controlled to lower value under the suitable condition, and stable electrolysis was conducted. Partial electrochemical reduction of Ti ions was not necessary. and a gas electrode was disused. Therefore, the process could be simplified in comparison to not only that in a chloride melt and also that in a fluoride melt by using H_2 gas oxidation as anodic reaction. The NaCl-KCl-NaF-KF salt was removed from the Ti deposit with water more easily than the LiF-NaF-KF salt.(3) High DC-current was applied through a CaF_2-CaO mixture containing TiO_2 in an electro-slag remelting apparatus. The mixture was melted by Joule heat. and Ti metal was obtained at the cathode on the bottom of the cell. It is concluded that this process is promising in principal, and that a sufficient heat must be supplied to actualize the process.