氧化物与氟化物的加入对氯化物熔盐体系电解制备Mg-La合金的影响

以石墨坩埚为阳极,钨棒为阴极,在750℃的MgCl2-LaCl3-KCl熔盐体系中,采用恒电位电解制备Mg—La合金。研究氧化物和氟化物的加入对电解的影响,通过XRD对部分Mg-La合金产物和电解渣进行表征。随着MgO或La203在熔盐电解质中加入量的增加,电流效率和所得合金产物的质量都减小,表明MgO和La203参与电解质中的反应。在加入的氧化物质量相同的情况下,MgO与La2O3相比对电流效率和合金产物质量的影响更明显。XRD研究结果表明：MgO或La2O3加入到熔盐电解质中后,有LaOCl生成,LaOCl电解渣的生成是氧化物对电解消极影响的主要原因。在本实验的的熔盐体系中,CaF2的加入对消除MgO的负面影响没有积极意义,这可能和镧化合物在熔盐电解质中的复杂反应有关。     

熔盐电脱氧法中氧离子在氯化钙熔盐中的 扩散动力学研究

本文以分子模拟为基础，构建了O2-/CaCl2的全原子模型，以Born-Mayer-Huggins（BMH）势函数对体系进行描述，研究了O2-在CaCl2熔盐的扩散动力学行为。结果表明：1073 K时O2-扩散系数为2.01×10-5 cm2/s，与F.D.Ferro经验公式的计算值一致；同时发现温度与O2-的扩散系数呈正相关关系，拟合得到O2-在CaCl2熔盐中的扩散活化能为15.6 kJ/mol。在微观结构方面，由于静电吸引的作用，熔盐中Ca2+会在O2-周围形成正电配位层，并束缚了O2-的扩散；O2-从形成的Ca2+配位层中逸出需要越过的能垒约为1.7 J。本文不仅揭示了O2-在CaCl2的动力学行为，也为计算机模拟指导研究改良熔盐配方提供研究基础。     

An electrochemical method for the preparation of Mg–Li alloys at low temperature molten salt system

Mg–Li alloys have been prepared by electrolysis in a molten salt electrolyte of 50% LiCl–50% KCl (mass%) at low temperature of 420–510 °C. The effects of electrolytic temperature and cathodic current density on alloy formation rate and current efficiency were studied. For the deposition of metallic lithium on the cathode consisting of solid Mg and liquid Mg–Li, both electrolytic temperature and cathodic current density have no obvious influence on current efficiency; while for the deposition of metallic lithium on the solid magnesium cathode, both electrolytic temperature and cathodic current density greatly affect alloy formation rate and current efficiency. The optimum electrolysis condition is—molten salt mixture, LiCl:KCl = 1:1 (mass%), electrolytic temperature: 480 °C, cathode current density: 1.13 A cm⁻². Mg–Li alloys with low lithium content (about 25 wt% Li) were prepared via electrolysis at low temperature following by thermal treatment at higher temperature.     

熔盐电解制备四元Mg-Zn-Li-Ca合金(英文)

在LiCl-KCl-MgCl2-ZnCl2-CaCl2熔盐体系中,以钼为惰性电极,在温度为943K时,直接电解制备Mg-Zn-Li-Ca四元合金。循环伏安研究表明,在LiCl-KCl熔盐体系中,添加MgCl2、ZnCl2和CaCl2后,Li的析出电位明显正移。计时电位研究表明,当阴极电流密度等于或者更负于-1.55A/cm2时,Mg、Li/Zn和Ca能够实现四元沉积。X射线衍射研究表明,恒电流电解可以制备出由不同相组成的Mg-Zn-Li-Ca合金。采用金相显微镜和电子扫描显微镜对合金样品进行表征。能谱分析结果表明,Mg元素和Ca元素在合金中分布均匀,而Zn元素主要分布在基体的边缘。     

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.     

电解废旧铝合金回收铝的电流效率(英文)

研究在AlC13-NaCl熔融盐体系中进行电精炼废旧铝合金回收金属铝。以铝合金为阳极,通过直流电沉积在铜阴极上得到铝涂层。在170°C、电流密度100 mA/cm2下电解4 h,得到的沉积物铝的纯度大约为99.7%,电流效率为44%~64%,每千克铝消耗电能3~9 kW·h。探讨阴极电流密度、电解质成分和电解时间及温度等对铝沉积电流效率的影响。结果表明:在AlCl3和NaCl摩尔比为1.3~1.9时,AlCl3和NaCl摩尔比对电流效率的影响很小,升高电解温度有利于提高电流效率;但是延长电解时间或增大电流密度会导致电流效率降低。电流效率的降低主要是由于沉积的铝呈现枝状晶或粉化而易从阴极上脱落到电解质中所致。     

Mechanism of chlorinating lanthanum oxide and cerium oxide with ammonium chloride

1　INTRODUCTIONThelightrareearthoressuchasbastnasiteandBeiyuneboitearetheoneswithlanthanumandceriumelementasmaincomponent (thecontentoflan thanumandcerium >85 % (massfraction) ) .General ly ,thelightrareearthoresaredecomposedbyacidoralkali,thentherareearthproductscouldbefurtherrecovered[1,2 ] .Someshortagesexistintheconven tionalprocessofrecoveringrareearth ,suchaslongflow sheet ,multi transferringformoftherareearthandsoon .Furthermore ,thewasteacidoralkaliandgasemissionsuchasHF ,SO2 pr…     

TC4钛合金熔盐电解法渗硼

采用熔盐电解法对TC4合金表面渗硼。用质量比为8：2的无水硼砂-无水碳酸钠熔盐体系在1500～4500 A/m²的电流密度下进行渗硼实验,利用XRD对渗硼试样表面进行物相分析,用扫描电镜观察渗硼试样的断面形貌并用能谱（EDS）进行元素分析,研究了电流密度对渗层结构的影响,并对TC4合金的渗硼机理进行了分析。结果表明,电流密度为3500 A/m²时渗硼效果较好,渗层外层结构均匀密实,主要物相是TiB₂,内层为TiB,渗层中还检测到少量V₂B₃。综合考虑实验结果及反应的标准吉布斯自由能计算推测出TC4合金渗硼时,在电流作用下,先在合金表面还原生成Na,然后Na将B₂O₃中的B置换,与合金的Ti反应生成TiB₂及TiB。     

Electrochemical mechanism of electrolysis codeposition of Mg-Sr alloy in molten salt

The electrochemical process of Mg-Sr codeposition was studied in MgCl₂-SrCl₂-KCl melts containing different MgCl₂ concentrations at 700 °C by cyclic voltammetry, chronopotentiometry and chronoamperometry. The results show that the actual precipitation potential of Sr reduces by nearly 0.5 V because of the depolarization effects of Sr activity reduced by forming Mg-Sr alloy. The codeposition potential condition of Mg and Sr to form Mg-Sr alloy is as follows: When electrode potential is more negative than ?1.5 V, the magnesium will precipitate; when electrode potential is more negative than ?2.0 V, the magnesium and strontium will both deposit. The control step of codeposition process of Mg and Sr is not diffusion control step. The codeposition current condition of Mg and Sr to form Mg-Sr alloy by chronoptentiometry is as follows: cathode current densities are higher than 0.71, 1.57 and 2.83 A/cm² in MgCl₂-SrCl₂-KCl melts with MgCl₂ concentrations of 2%, 5% and 10% (mass fraction), respectively.     

熔盐电解法的气体研究及其对电解的影响

采用离子色谱、火焰吸收等方法分析反应器中的残渣和尾气凝液,结果表明:残渣的主要成分为FeCl_2/FeCl_3、NiCl_2、CrCl_2/CrCl_3和CaCl_2,其中以铁的氯化物含量最高;凝液主要由HCl、HClO、H_2O以及金属氯化物所组成。分析认为反应器内的气体包括:Cl_2、HCl、HClO、H_2O、金属氯化物蒸气和通入的氩气等。模拟计算表明,在常用的1.0L/min的氩气流量下,难以将反应器内的HCl、HClO等腐蚀性气体及时排出反应器,它们与反应器内壁发生反应形成金属氯化物,对设备造成严重腐蚀,并且会对电解过程产生一定的影响。通过模拟计算不同流量的氩气在反应器内的流动状况,并结合尾气吸收实验,确定在2 h的预电解期,氩气通入量宜改为5.0 L/min。在不同的氩气通入方案下电解TiO_2发现,改进后的氩气通入方案有利于电解速度的提高,且设备的腐蚀情况有所缓解。     

熔盐电解法生产海绵钛的回顾和新技术开发

回顾了熔盐电解法生产海绵钛的研究 ,介绍了熔盐电解TiCl4生产海绵钛的工艺过程 ,重点提出一项在熔融CaCl2 中直接电解还原TiO2 生产海绵钛的新工艺。     

海绵钛熔盐电解制取高纯钛粉过程中离子价态、杂质及电结晶行为(英文)

以NaCl-KCl-TiClx为电解质,以海绵钛为原料进行熔盐电解提纯制取高纯钛粉。研究电解过程中离子价态、纯度及电结晶的演变规律。XPS分析表明,在电解前期、中期及后期,钛离子主要分别以+4、+3、+2价存在。在电解过程中,Si、Cr、Mn、Al杂质的含量基本恒定,而Fe、Cu、Ni杂质的含量逐渐降低,O、N、H元素的含量明显增加。在电解钛粉体内部,杂质元素主要分布在枝晶间所形成的"坑道"内。电解钛粉体形貌及粉体粒度受电解温度和时间的影响较大,温度升高及时间延长可增加钛粉体的粒度。透射电镜分析表明,电结晶的钛粉体不是单晶,而是由大量的纳米晶粒及亚晶粒组成的,晶粒尺度为100～500 nm。对电解机理进行了讨论。     

Modeling and simulation of neodymium oxide dissolution in molten fluorides

By combining the mass transfer mechanism of neodymium oxide with dissolution kinetics, a solution strategy for neodymium oxide dissolution was proposed to predict the dissolved neodymium oxide concentration during the process under complex flow field conditions. The factors affecting neodymium oxide dissolution were analyzed in detail. Aiming at the pulse feeding and continuous feeding modes in industrial practice, the characteristics of the dissolution process under the two feeding modes were compared. Simulation results showed that pulse feeding took shorter time to distribute evenly than continuous feeding. Finally, the dissolution time of single-particle neodymium oxide under static flow field conditions was compared with the literature results. Except for only one set of data with a maximum error of about 10%, the errors of other data are all within 5%.     

铝厂提高电流效率的研究

研究在各项技术条件下 ,如何提高电流效率。通过向电解槽中添加 5 %的氟化镁 ,并且在电解槽上安装盖板 ,这样可控制电解槽温度 ,从而将电解温度降低了 2 0℃。采用以上措施可以节省能量 ,试验的结果也表明电流效率提高了 2 %。     

Electrochemical Preparation of Mg-Li-A1-Er Alloys by Co-reduction in Molten Chloride

The electrochemical behavior of Mg,Li,Al and Er were investigated by electrochemical techniques in LiClKCl-MgCl2-AlCl3-ErCl3 melts at 823 K.The cyclic voltammetry and chronopotentiometry indicated that the co-reduction of Mg,Li,Al and Er occurs at current densities more negative than-0.89 A.cm-2.Er(III) under-potential deposited on pre-reduced Al electrode formed Al-RE alloys.X-ray diffraction(XRD) results indicated that Mg17Al12,Al2Er,Al2Er3 and Al4Li9 phases were prepared by galvanostatic electrolysis.ICP analyses of samples showed that lithium and aluminum contents of Mg-Li-Al-Er alloys could be controlled by concentration of AlCl3 and cathodic current density.     

The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors

The corrosion inhibition mechanisms of new cerium and lanthanum cinnamate based compounds have been investigated through the surface characterisation of the steel exposed to NaCl solution of neutral pH. Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to identify the nature of the deposits on the metal surface and demonstrated that after accelerated tests the corrosion product commonly observed on steel (i.e. lepidocrocite, γ-FeOOH) is absent. The cinnamate species were clearly present on the steel surface upon exposure to NaCl solution for short periods and appeared to coordinate through the iron. At longer times the Rare Earth Metal (REM) oxyhydroxide species are proposed to form as identified through the bands in the 1400-1500 cm⁻¹ region. These latter bands have been previously assigned to carbonate species adsorbed onto REM oxyhydroxide surfaces. The protection mechanism appears to involve the adsorption of the REM-cinnamate complex followed by the hydrolysis of the REM to form a barrier oxide on the steel surface.     

Electrolytic Preparation of Mg-La Alloy in Chloride Molten Salt: Effect of Electrolyte Composition

在MgCl2-LaCl3-KCl熔盐体系中,系统研究了恒电位电解过程中,电解质组成对平均电解电流、电解效率和合金成分的影响。用XRD、SEM和EDS对Mg-La合金样品进行了表征。随着初始电解质中LaCl3浓度的增加,平均电解电流逐渐降低。这是由于与MgCl2相比,LaCl3较低的电导率引起的。当LaCl3在初始电解质中的浓度为15%~20%（质量分数）时,电流效率超过90%。合金组成可通过改变电解质组成来调节。     

CaWO4-NaCl-CaCl2体系熔盐电解制备钨粉的表征与电化学分析

通过熔盐电解法从CaWO4-NaCl-CaCl2体系制备出金属钨粉,采用X射线衍射仪(XRD)、电子扫描显微镜(SEM)和能谱分析仪(EDS)对钨粉的形貌和相组成进行表征。在试验数据的基础上计算电流效率,通过分析电解过程中形成的中间产物,讨论电解过程中的电极反应,采用循环伏安法和方波伏安法分析体系的基本热力学性质。结果表明:在750℃、槽电压2.5 V下经5 h以上电解可制备出纯度达到99%、平均粒度低于2μm的金属钨粉,实验中的电流效率可达到80%;电解过程的电极反应不可逆,浓差极化是体系电解速率的主要阻力。