Current efficiency of recycling aluminum from aluminum scraps by electrolysis

Extracting aluminum from aluminum alloys in AlCl3-NaCl molten salts was investigated. Al coating was deposited on the copper cathode by the method of direct current deposition using aluminum alloys as anode. The purity of the deposited aluminum is about 99.7% with the energy consumption of 3-9 kW＆#183;h per kg Al, and the current efficiency is 44%-64% when the deposition process is carried out under 100 mA/cm2 for 4 h at 170 ＆#176;C. The effects of experimental parameters, such as molar ratio of AlCl3 to NaCl, cathodic current density and electrolysis time, on the current efficiency were studied. The molar ratio of AlCl3 to NaCl has little effect on the current efficiency, and the increase of deposition temperature is beneficial to the increase of current efficiency. However, the increase of current density or electrolysis time results in the decrease of current efficiency. The decrease of current efficiency is mainly related to the formation of dendritic or powder deposit of aluminum which is easy to fall into the electrolyte.

Preparation of Mg-Li alloys by electrolysis in molten salt at low temperature

A new technology for preparation of low cost Mg-Li alloys was studied. The alloys were prepared by electrolysis in molten LiCl-KCl （weight ratio is 1：1） electrolyte with Mg rod severing as the consumed cathode. Main factors that affect current efficiency were investigated, and optimal electrolysis parameters were obtained. Mg-Li alloys with low lithium Content （about 25%） were prepared by the unique method of a higher post-thermal treatment temperature after electrolysis at low temperature. The results showed that the electrolysis can be carried out at low temperature, which resulted in reducing preparation cost due to energy saving. The new technology for the oreoaration of Mg-Li alloy by electrolysis in molten salt was laroved to be feasible.

Current efficiency in electro-winning of lanthanum and cerium metals from molten chloride electrolytes

The objective of this study is to prepare lan- thanum and cerium metals by fused salt electrolysis of their anhydrous chloride in molten media such as LiCl-KCl, NaCl-KCl, KCl, NaCl, and LiCl and to characterize the metal deposit by X-ray diffraction, energy dispersive X-ray fluorescence, and inductive coupled plasma-atomic emis- sion spectroscopy. Deposit metal of purity more than 99 % was obtained in each of the experiments. The entire process starting from preparation of anhydrous lanthanum/cerium chloride to electrolysis yielding of metal deposits has been described. The effect of process parameters such as tem- perature, electrolyte composition, and current density on the current efficiency was studied. All these parameters were varied to get the highest current efficiency and metal yield. The major non-rare earth impurities with the deposit are found to be Fe, Cr, and Ni along with - 1× 10^-3 of total gaseous impurities.

Effect of oxide and fluoride addition on electrolytic preparation of Mg-La alloy in chloride molten salt

Mg-La alloys were prepared by constant voltage electrolysis in the molten salt system of MgC12-LaC13-KC1 at 750℃, with a graphite crucible as the anode and a tungsten rod as the cathode. The effect of oxide and fluoride addition on the electrolysis was investigated comprehensively. X-ray diffraction （XRD） was used to characterize some of the Mg-La alloy products and the sludges. As the content of MgO or La203 in the electrolyte increased, both the current efficiency and the mass of alloy product decreased, indicating that both MgO and La203 may take part in the reactions in the electrolyte. When the same mass of the oxide was added, compared with La203, MgO had a more pronounced effect on both the current efficiency and the mass of alloy product. XRD studies confirmed the formation of LaOC1 when MgO or LazO3 was added into the electrolyte. The formation of LaOCl sludge would be the main reason for the negative effect of the oxide addition on both the current efficiency and the mass of alloy. In the electrolytic system, the addition of CaF2 was not helpful to suppress the negative effect of MgO on the electrolysis, probably due to the complex reactions of the La compounds in the electrolyte.

Preparation of Mg-Li-Sm alloys by electrocodeposition in molten salt

Electrocodeposition of Mg-Li-Sm alloys was investigated in molten KCl-LiCl-MgCl2-SmCl3-KF system.The effects of electrolytic temperature and cathodic current density on current efficiency were studied and optimal electrolysis parameters were obtained.The optimum electrolysis condition was a molten salt mixture of LiCl:KCl =50:50(wt.%),electrolytic temperature:660 oC,cathode current density:9.5 A/cm2 and electrolysis time of 40 min.The current efficiency reached 77.3%.X-ray diffraction(XRD) and scanning elec...

Enhanced preparation of dendritic metallic vanadium in recyclable NaCl-KCl-VCl_(2) molten salt by V_(2)CO electrolysis

A promising method for the preparation of pure metallic vanadium via V_(2)CO anode electrolysis was proposed and confirmed.The simple and controllable synthesis of a molten chloride salt containing VCl_(2) by an insitu reaction between VCl_(3) and metallic vanadium was verified through thermodynamic analysis and experiments.NaCl-KCl-VCl_(2) molten salt exhibited excellent recycling performance and could be repetitively used to prepare metallic vanadium by V_(2)CO electrolysis.The V^(2+) ions remained in the molten salt after electrolysis.The electrolysis conditions,such as the cathode diameter,current density,V^(2+) ion concentration,and temperature,were optimised to maximise the current efficiency.Electrolysis was also simulated to reveal the regulatory mechanism.The highest current efficiency was 85%.The purity of metallic vanadium was up to 99.8%.In this study,an easy and efficient preparation of pure metallic vanadium was achieved.

Optimal V_(2)O_(3) extraction by sustainable vanadate electrolysis in molten salts

Recently,an environmentally friendly electrolysis process of soluble vanadates is proposed and successfully confirmed for V_(2)O_(3) extraction.In this paper,the solubilities of various vanadates(i.e.NaVO_(3),Na_(4)V_(2)O_(7) and Na_(3)VO_(4))in NaCl molten salt are measured.The dependences of V_(2)O_(3) extraction on vanadate form,anode material and molten salt system are studied.A long-term electrolysis is carried out.The result indicates that the solubilities of all vanadates are high and meet electrolytic requirements.Compared to Na_(4)V_(2)O_(7) and Na_(3)VO_(4),NaVO_(3) exhibits larger current efficiency and lower electricity consumption.By using SnO_(2) anode instead of graphite anode,the current efficiency of NaVO_(3) electrolysis can be increased to 58.1%and carbon pollution is avoided at 700℃.The extraction rate of V_(2)O_(3) reaches 81.3%after long-term electrolysis of 51 h.This work optimizes the electrochemical preparation process of V_(2)O_(3) from various vanadates and contributes to the improvement of current efficiency and extraction rate.

基于模糊天牛须PID的稀土电解温度浓度解耦控制

稀土电解过程中电解槽内温度是影响出料金属品质、电解能耗的关键条件,同时槽内氧化物浓度决定了出料金属的效率和电解过程的稳定性。但实际电解槽内化学反应多、过程复杂,电解槽温度、熔盐氧化物浓度两者存在非线性的耦合关系。电解槽模型具有高滞后、强耦合、时变系统的特点,单独以电解温度或氧化物浓度作为被控变量难以保证出料金属的品质。以6 kA氧化钕电解温度、氧化物浓度作为输入,阴极电流密度、氧化物下料率作为输出,对输出变量进行解耦补偿,实现多变量解耦控制,从而提高氧化钕电解的品质;通过模糊PID控制器引入专家知识库对温度、浓度实现有效控制,改善了以往稀土电解过程中控制变量单一效果不理想的难题;借助天牛须的寻优迭代能力优化模糊PID的初始参数。利用Simulink平台对模糊PID解耦控制器和常规PID控制器进行仿真对比实验,实验结果表明:模糊PID解耦控制系统较单一温度PID控制效果更好,超调量提高了6%,系统响应速度提高25%。

熔盐电解法制备铝锂中间合金

研究在LiCl-LiF-Li2CO3纯锂盐体系中下沉式铝液阴极槽结构电解生成铝锂中间合金的工艺过程,尤其是以Li2CO3为原料代替LiCl的电解过程。采用熔盐电解监控仪测量电解过程中的反电动势、槽电压、电流等工艺参数及电解波形图,通过电位控制法调节Li2CO3的加料周期,同时根据得到的合金产品中的锂含量探讨影响电流效率的因素。结果表明,反电动势随电流密度增加而增大,加入2%的Li2CO3可使反电动势降低0.5V;通过控制电位法测得加料周期为15min;在680℃、电流密度为0.62A/cm2的条件下持续电解3h,最终制得了锂含量高达7.93%的铝锂合金,电流效率可达74.1%。

太阳能电池及多晶硅的生产

在简述太阳能电池原理和发展的基础上,分析了太阳能电池用多晶硅的生产方法.认为:改良的熔盐电解法和熔盐三层电解精炼法有可能直接制取太阳能级多晶硅,此法一旦研究成功,将大幅度地降低太阳能级多晶硅生产成本,应引起人们的关注.

熔盐电脱氧制多晶硅过程电流效率的影响因素

电流效率是熔盐直接电解脱氧制备多晶硅的一项重要指标,它涉及到电解槽的产量和电耗。如何提高熔盐电解的电流效率对多晶硅的单位时间产量、降低单位电耗等具有重要意义。采用CaCl2为电解质、SiO2粉末压制片为阴极及自制石墨棒为阳极进行了实验研究。在具体实验中测定了制备多晶硅过程中电流效率随电解时间、温度、电流密度及电极间距的变化关系。结果表明,当电解时间为6～10h、电解温度为800～900℃、电流密度为0.78～1.20A/cm2、电极间距为4～7cm时,电解效率较高。

熔盐电解法制备铝镁合金过程电流效率和反电动势研究

以氧化镁为原料,在MgF2-LiF-KCl电解质体系中采用熔盐电解制备铝镁合金,考查电解时间、电流强度对电流效率以及合金中镁含量的影响,并采用连续脉冲—计算机法测量电解过程反电动势的变化。结果表明,电流效率随电流密度和电解时间的增加先增大后减小;镁含量随电流强度的增加先增大后减小,随电解时间逐渐增大。在3A的电流强度下电解2h的电流效率达87%,加料前后平均反电动势降低0.5V,氧化镁(1%)的加料周期约45min。铝镁合金中镁浓度分布比较均匀,无明显偏析现象。

电解法制备硼粉过程电流效率的影响因素

电流效率是电解法制备单质硼的一个重要生产指标,它涉及到硼电解槽的产量和电耗。在电解槽型的设计过程中,如何提高熔盐电解的电流效率对于硼粉的单位时间产量、降低单位电耗等主要技术经济指标具有重要的意义。文中采用氟化钾-氯化钾-氟硼酸钾体系,进行了实验研究。在电解槽内测定了制备过程中电流效率随电解温度、电流密度、电极间距离、电解时间的变化关系。结果表明:当电解温度为760—790℃、电流密度在0.8—1.14 A/cm2、电解时间为2.5—3 h、极间距离为4 cm时,电解的电流效率最高。

熔盐电解制备细颗粒钛粉研究

在氯化物熔融盐中电解海绵钛制取细颗粒钛粉,研究了可溶钛浓度、阴极电流密度以及加料方式等因素对阴极产品颗粒形貌及粒度的影响,制备了平均粒度约为60～70μm的细颗粒钛粉。实验结果表明,电解初期形成块状结晶,电解后期为树枝状;可溶钛浓度对钛粉粒度影响显著;采用气相加料容易使钛在熔盐表层形成鳞片状结构。

氟化物熔盐共电沉积制备Gd-Zr-Mg合金的研究

采用GdF3-LiF-BaF2为电解质熔体,Gd2O3、ZrO2及MgO混合氧化物为原料共电沉积Gd-Zr-Mg中间合金,考察了电解温度、阴极电流密度及混合氧化物原料中ZrO2的含量对电解电流效率及所得中间合金中Zr含量的影响.研究表明:电流效率随温度和电流密度增大均先增后减,随混合氧化物原料中ZrO2含量增大则减小;电解得Gd-Zr-Mg合金中Zr含量随电解温度和混合氧化物原料ZrO2含量的增加而增加,随阴极电流密度的增加则是先增后减,电流效率可达57%,Zr含量能达到10%～11%.

氟化物熔盐共电沉积制备Gd-Mg中间合金研究

以混合Gd2O3-MgO为原料,在GdF3-LiF-BaF2-CaF2氟化物熔盐体系中研究一步法共电沉积制备了Gd-Mg中间合金,探讨了电解质成分、原料Gd2O3-MgO中Gd/(Gd+Mg)、电解温度等对电流效率的影响.研究表明,共电沉积得Gd-Mg中间合金以GdMg相存在,成分均匀;随电解质成分GdF3含量、原料Gd2O3-MgO中Gd/(Gd+Mg)、电解温度、电流密度的提高,电流效率均先升后降;当电解质GdF3含量为85wt%、原料Gd2O3-MgO中Gd/(Gd+Mg)为86wt%、电解温度为1 050℃、体电流密度0.10 A/cm3时,电流效率最高达到80%.

熔盐电解法制备高纯钛粉

以海绵钛作可溶阳极,纯钛板为阴极,NaCl-KCl-TiClx混合熔盐作电解质,在电解温度为900～980℃、阴极电流密度为0.1～0.6A/cm2、初始可溶钛浓度2%～8%的条件下,电解24h制备高纯钛粉,研究初始可溶钛浓度对钛粉中杂质元素含量的影响,以及电流密度和初始可溶钛浓度对电流效率及钛粉形貌的影响。结果表明,钛粉杂质含量完全达到高纯钛粉的标准,提高初始可溶钛浓度可降低杂质含量;在较高的阴极电流密度以及高的初始可溶钛浓度下电解效率较高;在阴极电流密度较高时钛粉为细小的树枝状晶体,而在阴极电流密度较低时得到较粗大均匀的结晶粉体。

熔盐电解法制取Al-Li母合金

以LiCl KCl为电解质 ,铝为阴极 ,在 45 0℃下采用熔盐电解法直接制取铝锂母合金 ,并研究了熔盐电解法生产铝锂合金的工艺条件。结果表明 :随着电流密度、电解时间的适当增加 ,合金中锂的含量逐渐增加 ;但是过大的电流密度和过长的电解时间会导致阴极出现开裂现象 ,使工艺条件不稳定 ,影响产品质量。

SrCl_2-KCl-SrF_2体系中熔盐电解法制备铝锶合金

以SrCl2为原料,在70%SrCl2-29%KCl-1%SrF2体系中电解生产Al-Sr合金。考察了电解温度、电流密度和电解时间等条件对电流效率和合金锶含量的影响。通过控制工艺条件,可以生产锶含量在0～10%的Al-Sr合金,其物相主要为Al与Al4Sr。

熔盐电脱氧法制备难熔金属及合金的研究进展

介绍了熔盐电脱氧法制备难熔金属及合金的基本原理和工艺,分析了熔盐电脱氧法的优势及目前存在的主要问题,归纳了采用熔盐电脱氧法制备难熔金属及合金的研究进展,指出了该制备工艺的发展趋势,并对其推广应用和实现大规模工业化前景等进行了讨论。