摘要
现有难熔金属及合金的制备工艺复杂、成本高、污染环境。因此,开发一种流程短、成本低且对环境友好的金属制备方法是研究者共同的目标。本文回顾并总结了金属钽、铬、钛及钛合金的制备方法,分析其相关工艺的特点,利用固体透氧膜(SOM)法对金属氧化物直接制备难熔金属及合金进行了研究。
SOM法以固体透氧膜管内碳饱和的铜液为阳极,在所选择的熔盐中对氧化物阴极进行电解还原。只传导氧离子的固体透氧膜管将阳极与熔盐隔离开,因膜管对离子的选择性作用,使得参与阳极反应的阴离子只有O2-,通过控制电极电位保证特定金属离子在阴极选择性析出,参与电解反应的是金属氧化物而非其它物质。
论文对熔盐性质、透氧膜的稳定性、阴极制备、电解影响因素及电解机理等方面进行了研究,并利用三相界面反应机制描述了SOM法的电化学过程。
对熔盐的物性研究表明,1100℃下,55.5MgF2-44.5CaF2(wt%)熔盐挥发率小于5.4×10-7g/cm2·s,粘度为11.8 mPa·s,电导率为5.2 S·cm-1;CaCl_2熔盐的挥发率为1.9×10-6g/cm2·s,粘度为3.4mPa·s,电导率为3.6 S·cm-1;两类熔盐的粘度和挥发率低、电导率高,满足实验要求。
在不同掺杂比例下,对自制的固体透氧膜管研究表明,8%mol Y_2O_3部分稳定的ZrO2管结构致密,光洁度好,具有良好的电性能,在1000～1300℃电导率为0.18～0.47S?cm-1,实验过程电化学性质稳定。
对阴极制备及电解影响因素的研究表明,在4MPa的成型压力下,经1100～1150℃烧结2小时的Ta_2O_5和Cr_2O_3片均具有良好的电化学活性;电解2小时阴极产物中的氧含量可达到较低值;随着电解时间延长,金属颗粒会发生异常长大;当电解温度小于1100℃时,还原速度会急剧降低。若烧结温度升高到1300℃,电解Ta_2O_5试样出现致密的内核,而电解Cr_2O_3试样出现金属外壳。在产物具备一定强度的前提下,Ta_2O_5阴极的孔隙率和颗粒尺寸的合理范围为30～40%和0.6～1.0μm。Cr_2O_3阴极的孔隙率和颗粒尺寸的合理范围为40～50%和≤1.0μm。
对SOM法与FFC法制备金属铬进行了实验对比。结果表明,SOM法具有较高的过电位,还原速度快,电流效率高,不会发生副反应。当电压从3.0V升到3.5V时,反应速度理论上提高7.7倍。
利用遵义钛厂提供的含钛废渣进行了制备钛及其合金的研究。电解铁钛废渣,可获得TiFe和TiFe2合金;电解高钛废渣,可获得纯的金属钛。
分析了体系中的离子迁移行为,研究了SOM法的电解机理,结果表明Ta2O5和Cr2O3电极的还原均分两步完成,Ca参与阴极还原是有利的,形成的中间产物寿命极短。通过分析试样内三相界线的分布及三相界线对电流的影响,证明了SOM法的还原过程符合三相界面反应机制。
SOM法金属氧化物直接制备金属及合金,工艺流程短,能耗低,绿色环保,可以实现连续化生产,该冶金新工艺的开发对我国各类复合矿的开发利用具有重要的意义。
The existing pyrometallurgical process to prepare refractory metals and their alloys is complex, expensive, energy intensive and probably polluting. Therefore, it is common desirable to develop a simple, low-cost and environmentally sound process to prepare metal. The paper reviewed and summarized the methods for preparation of Ta, Cr, Ti and Ti alloy and analyzed their shortages. As a result, extracting of refractory metals and alloys from their respective oxides directly using SOM (Solid Oxide Membrane) process have been investigated.
The electrolysis reduction of oxides cathode is performed by SOM process in the selective molten salt, which liquid copper, saturated with graphite powders and encased in a one-end-closed solid oxide membrane tube, acted as the anode. The anode and the molten are separated by SOM which conducts oxygen ion only. As a result, only oxygen ions are oxidezed at the anode. The desired metal cations are reduced selectively at the cathode through control the electrode potential. Therefore, only metallic oxides take part in electrolytic reaction.
The property of the fluxes, the stability of solid oxide membrane, the formation of cathode pellets, the parameter of electrolysis and the electrolytic mechanism are studied in this paper respectively. And the electrochemical reduction mechanism of SOM process was depicted by using the three-phase interlines react mechanism. The study for property of the fluxes showed that the volatility, viscosity and conductivity of the molten 55.5MgF2-44.5CaF2(wt%) are less than 5.4×10-7g/cm2·s, 11.8mPa·s and 5.2 S·cm-1, and of the molten CaCl2 are 1.9×10-6g/cm2·s, 3.4mPa·s and 3.6S·cm-1, respectively. The two fluxes have high conductivity, low viscosity and volatility, which can satisfy the demand of experiment.
The study for membrane tube with self made at different doping showed that the 8%mol Y2O3 stabilized ZrO2 tube has compact microstructure, good smooth finish and electro properties. The conductivity is between 0.18 and 0.47S?cm-1 at the temperature of 1000℃to 1300℃. The electrochemical property of the cell system kept stability in the course of experiment.
The Ta2O5 and Cr2O3 pellets formed at 4 MPa and sintered at 1100~1150℃for 2 hours exhibited good electrochemical performance and the oxygen content of the products were low after electrolyzing for 2 hours at 1100℃. The metallic particles could increase obviously with electrolytic time. However, the rate of reaction declined rapidly, when the electrolytic temperature was lower than 1100℃. When the sintering temperature increase to 1300℃, the compact core has been shown in electrolyzed Ta2O5 samples, but the compact crust was occurred in the Cr2O3 samples. Under the premise of electrolysis samples with strength, it is suggested that rational range of the porosity and particle size of Ta2O5 cathode should be 30 to 40% and 0.6 to 1.0μm, and of Cr2O3 cathode should be 40 to 50% and less than 1.0μm, respectively.
Ti and Ti alloy directly made from Titaniferous residue (Zunyi titanium plant) in the molten CaCl2 (1100℃) has been investigated by SOM process. The results showed that the alloys of TiFe and TiFe2 were obtained from Ti-Fe residue, the pure Ti was obtained from titanium-rich residue after electrolyzed for 6 hours respectively.
The ionic migration action and the electrolytic mechanism during the operating of SOM process are investigated. The results showed that the electrochemical reduction of Ta2O5 and Cr2O3 pellets in molten CaCl2 are achieved via two steps. The reaction with Ca participated in is beneficial to reduction of cathode pellets, which the intermediate products are conductive with very short life. The distributing of three-phase boundary inside of pellets and the influence of three-phase boundary on current are dicussed. Which proved the electrochemical reduction of the SOM process obeys the three-phase interlines (3PIs) reaction mechanism at the metal/oxide/electrolyte interface.
SOM process is an emerging short-flow technology for extraction of metals directly from their oxides, which is environmentally friendly, less energy cost, and operating continuously. The development of SOM process as a new metallurgy technology has significance for exploitation and utilization with different composite ore resource in China.
引文
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