熔盐电脱氧法制取Ti的反应机理

通过低电压电解实验、不同阴极电解对比实验和反电动势测定实验,并结合循环伏安法研究了熔盐电脱氧法制取金属Ti过程中阴极的还原过程。结果表明,还原过程是分步进行的。TiO2先被还原为Ti3O5或Ti2O3,再进一步被还原为Ti3O、Ti2O、TiO或金属Ti。另外,阴极进行的主要电极反应是TiO2的直接电还原反应,同时在阴极也存在一定的钙热还原反应,只是反应强度较弱。另外,分别以钼丝和二氧化钛为研究电极,进行了循环伏安曲线测定。     

熔盐电脱氧法制取Ti机理的研究

通过低电压电解实验和不同阴极电解对比实验,并结合循环伏安曲线研究了熔盐电脱氧法制取金属Ti过程中阴极的反应机理。结果表明,在没有金属Ca生成的情况下,TiO2阴极可以直接还原,生成低价钛氧化物。在正常电解的情况下,阴极进行的主要电极反应是TiO2的直接电还原反应,同时在阴极也存在一定的钙热还原反应,只是反应强度比较弱。     

熔盐体系中电沉积制备TiB2镀层的研究现状

介绍了熔盐体系中电沉积制备TiB2镀层技术中熔盐的选择、电镀工艺和参数的选择，概述了不同熔盐体系中B离子、Ti离子在阴极沉积的电化学机珲以及TiB2的合成机理，论述了TiB2惰性阴极在铝电解工业中的研究现状，最后分析了熔盐体系中石墨电极上制备TiB2镀层的可行性。     

钛提取技术进展

对传统和新发展的各种钛提取技术的基本原理、工艺特点及进展进行了回顾.介绍了目前国内外正在开发或改进的钛生产工艺,其中包括二氧化钛的直接电化学还原法、Armstrong(ITP)法、钙热还原法、金属氢化物还原法、四氯化钛熔盐电解还原钛、SOM法等,指出新工艺在工业应用中存在的问题.作者认为:由于传统的Kroll法生产成本高,限制了钛的应用,只有开发新的、连续化的生产工艺,才能从根本上达到降低生产成本的目的.     

钙热还原二氧化钛的钛粉制备及其中间产物CaTiO3的成因

通过热力学计算以及XRD、SEM和EDS等测试手段,研究TiO2钙热还原制备钛粉过程中钛酸钙(CaTiO3)的形成原因。热力学计算表明:当温度高于800 K时,添加剂CaCl2水解产物CaO与TiO2生成CaTiO3的反应以及还原副产物CaO与TiO2生成CaTiO3的反应均满足反应发生的热力学条件。实验研究表明:CaTiO3的生成主要是由添加剂CaCl2水解生成的CaO与TiO2烧结反应所致,CaTiO3的量随着CaCl2添加量的增加而增加,且CaTiO3更容易被还原为金属钛。当CaCl2与TiO2的质量比约为1:4时、在1 273 K下还原时间为6 h时,反应过程中的CaTiO3被完全还原为金属钛粉,该粉末具有不规则外形,颗粒粒径为8~15μm。经EDS分析,金属钛粉中钛的质量分数达到99.55%。     

TiO2电化学还原法提取金属钛的阴极制备工艺

研究TiO2电化学还原法提取金属钛的阴极制备参数——烧结温度和烧结时间。采用SEM、EDS等方法研究烧结温度、烧结时间对TiO2阴极微观结构、孔隙率的影响及不同烧结条件下TiO2阴极电解产物结构和氧含量的变化。结果表明：烧结条件主要影响电极的粒度大小、孔隙尺寸和孔隙分布：在较高温度下烧结较长时间获得的电极片粒度较粗,而孔隙率的变化比较复杂。电极的颗粒尺寸、孔隙率直接影响脱氧率：粒度较小的电极在试验条件下可被充分还原;电极中的开孔和闭孔都有利于电化学还原过程的进行。在1000~1100 °C下烧结4 h获得的TiO2阴极脱氧效果较好。     

TiO2电极中O2-的形成及迁移过程研究

采用融盐电解法,在900℃熔盐CaCl2中以烧结TiO2为阴极,石墨棒为阳极制备金属钛。研究O2-在TiO2电极中的形成及其迁移过程。结果表明:实验高温促使TiO2结构中氧空位的形成及O2-产生;O2-通过氧空位从阴极内部迁移到表面,钛酸钙是电解过程的必然中间产物,阴极表面生成的致密金属层钛阻碍O2-从阴极内部往表面的迁移。     

金属钛制备方法的新进展

简要分析了金属钛的生产方法，指出：由于传统的Kroll法生产成本高，限制了钛的应用，只有开发新的、连续化的生产工艺，才能从根本上达到降低生产成本的目的。系统地总结了目前国内外正在开发或改进的钛生产工艺，其中包括二氧化钛的直接电化学还原法、钙热还原法、ITP法、导电体介入反应法、熔盐电解法以及金属氢化物还原法，指出了二氧化钛的直接电化学还原法是一种低能耗、无污染的绿色生产新工艺，最有希望取代传统的Kroll法。     

制钛过程中阴极钙钛矿的形成与阳极溢出气体间的关系

采用FFC剑桥工艺在熔融CaCl₂中电解二氧化钛时,钙钛矿是阴极上不可避免形成的相。本文研究了在制备钛的过程中,阴极钙钛矿的形成与阳极释放气体的关系。结果表明,阴极上相的形成主要有三个阶段,包括钙钛矿的形成、钙钛矿的脱氧及钛的低价氧化物脱氧为TiO、和TiO到Ti的脱氧。尽管分解电压低于CaCl₂,但阴极形成的钙钛矿与从阳极释放的气体密切相关。由于短时间内钙钛矿的形成造成过电压,因而阳极释放出氯气,氯气的量取决于TiO₂和电解过程中产生的不同低价钛的量。当钛的低价氧化物介于Ti₃O₅和TiO₂之间时,在第一脱氧阶段TiO₂和氯的质量比为9：2到46：2。在氯气释放的过程中阳极没有明显的消耗。钙钛矿的形成和Ti₂O的脱氧是在熔融CaCl₂中电解制备钛的主要限制性环节。从TiO₂到Ti的总电流效率是24.07％。目前第一阶段的电流效率在22.37％~44.74％之间,第二阶段在30.18％~37.72％之间。     

Effect of electrolysis voltage on electrochemical reduction of titanium oxide to titanium in molten calcium chloride

The electrochemical reduction of solid TiO2 directly to solid metal is a ptomising alternative to the current Kroll process. The present work is aimed at studying the effect of electrolysis voltage on the rate of electrochemical reduction. The products of electrochemical reduction of TiO2 and Ti2O were examined using the scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The results show that Ti2O was reduced to low valent titanium oxide at 1.5 -1.7 V, which was the result of ionization of oxygen. TiO2 and Ti2O were reduced to titanium metal at 2.1-3.1 V, which was the co-action of ionization of oxygen and calciothermic reduction. The oxygen content decreased rapidly with voltage increasing from 2.1 to 2.6 V, while it changed little from 2.6 to 3.1 V. The optimized cell voltage was 2.6-3.1 V.     

铝在NaCl－AlCl_3熔盐体系中的电化学沉积

采用循环伏安法研究了铝在融熔氯化钠—氯化铝体系中的阴极电化学沉积过程。在碱性熔体中阴极还原质点为ＡｌＣｌ４在酸性熔体中还原质点为Ａｌ２Ｃｌ７，而ＡｌＣｌ４通过溶剂平衡反应来影响铝的沉积过程。Ａｌ２Ｃｌ７的还原反应是准可逆的，反应机理复杂，可能是前置化学步骤或自催化反应。     

TiO_2直接电解还原过程的研究

采用SEM、EDS、XRD等方法对TiO2直接电化学还原产物进行分析,指出TiO2电极的还原是从外向内由高价到低价再到金属逐步进行的。对还原过程中电流、还原气相产物的分析结果表明:还原过程电流效率低,并且电流效率随电解时间延续而降低,阳极产物CO、CO2与阴极中间产物Ca发生副反应以及副反应产物炭黑造成电流短路是电流效率低的主要原因。提高电流效率的途径有两条:一是增大阴、阳极间距,减小副反应的发生;二是使电解池表面熔盐不断导出,或采取某一隔离措施,使副反应产生的炭黑在阴、阳极之间不造成电流短路。     

Characteristics of an electrochemical reduction of Ta2O5 for the preparation of metallic tantalum in a LiCl–Li2O molten salt

The electrochemical reduction of Ta₂O₅ in a LiCl–Li₂O molten salt system has been carried out in an electrolytic cell with an integrated cathode assembly. During the electrochemical run, Ta₂O₅ reacts chemically with Li₂O to form LiTaO₃. The chronopotentiometry method was used to prepare the metallic tantalum from Ta₂O₅. The electrolysis of Li₂O and the reduction of Ta₂O₅ and/or LiTaO₃ take place simultaneously at the cathode part of an electrolysis cell. The recycle of Li₂O by an O²⁻ diffusion occurs in the cell. The results suggest that the metallic tantalum is prepared successfully by an electrochemical reduction in the LiCl–Li₂O molten salt.     

熔盐中电解钛铁矿制备TiFe合金

通过在CaCl2熔盐中电解钛铁矿制备TiFe合金,研究了熔盐电解钛铁矿的反应过程,分析了电解产物的成分及电解效率。结果显示,钛铁矿的还原经历了优先生成Fe到逐步形成TiFe2、TiFe的合金化历程,中间产物包括 CaTiO3、Fe2TiO4、TiO。反应最先生成的合金是TiFe2合金,通过Ti和TiFe2的互扩散最终转变成TiFe合金, 说明扩散是反应的控制步骤。相同电解条件下,钛铁矿较混合氧化物难电解。这是由于钛铁矿颗粒较大,其杂质是固溶到钛酸铁中的,脱氧更难,电解效率较低     

内蒙古发现大型富钛矿床

采用循环伏安法和计时电流法研究了700℃时LiF-NaF-KF-K2TiF6熔盐中Ti（Ⅳ）在铂电极上阴极电化学还原机理以及电结晶过程。结果表明：Ti（Ⅳ）的电化学还原机理为三步骤电荷传递反应：Ti（Ⅳ）＋e→Ti（Ⅲ）；Ti（Ⅲ）＋2e→Ti（Ⅰ）；Ti（Ⅰ）＋e→Ti（0），且阴极过程可逆：电结晶过程为瞬时形核。     

Electrochemical process of titanium extraction

A wide variety of processes are being pursued by researchers for cost effective extraction of titanium metal. Electrochemical processes are promising due to simplicity and being less capital intensive. Some of the promising electrochemical processes of titanium extraction were reviewed and the results of laboratory scale experiments on electrochemical reduction of TiO2 granules were brought out. Some of the kinetic parameters of the reduction process were discussed while presenting the quality improvements achieved in the experimentation.     

Electrochemical decomposition of SiO2 pellets to form silicon in molten salts

Direct electrochemical reduction of porous SiO₂ pellets in molten CaCl₂ salt and CaCl₂-NaCl salt mixture was investigated by applying 2.8 V potential. The study focused on the effects of temperature, particle size of SiO₂ powder starting material and the behavior of cathode contacting materials during electrochemical reduction process. The starting materials and the electrolysis products were characterized by X-ray diffraction analysis and scanning electron microscopy mainly. The studies showed that smaller particle sizes and higher temperatures had slightly positive effects in increasing the reduction rate within the ranges covered in this study. The results were interpreted from variations of current and accumulative electrical charge that passed through the cell as a function of duration of electrochemical reduction under different conditions. Microstructures and compositions of the reduced pellets were used to infer that electrochemical reduction of SiO₂ in molten salts may become a method to produce silicon that could be used in solar energy utilization. Furthermore, X-ray diffraction analysis results indicated that the silicon produced at the cathode reacts with contacting materials; nickel, and iron in stainless steel to form Ni-Si and Fe-Si compounds due to very reactive nature of silicon especially at high temperatures.     

混合缓蚀剂对铜合金腐蚀性能的研究

利用恒电位法，研究了8-羟基喹啉与MBT不同浓度配比的混合缓蚀剂对铜合金的缓蚀效率的影响.通过极化曲线分析各种因素对缓蚀率的影响，从而找到缓蚀效果最好的配比.实验证明：混合缓蚀剂的缓蚀效率与浓度没有线性关系，而与一定的配比有关.       

熔盐电脱氧法制备ZrMn2储氢合金

采用熔盐电脱氧法,由MnO2和ZrO2混合氧化物直接合成ZrMn2合金。研究烧结温度、电解电压及电解时间等工艺参数对产物组成的影响。在900°C的CaCl2熔盐中,经900°C烧结的混合氧化物阴极在3.1 V恒电压下电解12 h,可制备出纯相的ZrMn2合金。XRD和循环伏安结果表明,在电解过程中,Mn-O化合物首先还原成单质Mn,ZrO2和CaZrO3再在单质Mn表面还原,并与其合金化,形成ZrMn2合金。以粉末微电极为工作电极,循环伏安测试结果表明,所制备的ZrMn2合金表现出良好的电化学储氢性能。     

Effect of TiO2 cathode performance on preparation of Ti by electro-deoxidation

To resolve the problem of low current efficiency and low reaction rate when preparing metal by electro-deoxidization method, various contents of CaO and CaCO3 were added into the TiO2 powder, which were compacted into pellets and sintered, and then conducted as the cathode. The morphology and contents of the cathode and products were studied by scanning electron microscopy and X-ray diffractometry, the effect of the additives were studied. The results show that formation of calcium titanate and change of microstructure within the cathode enhance the velocity of the direct electrochemical reduction of solid TiO2 to Ti.