Bi(Ⅲ)在NaCl-KCl熔盐体系中的电化学行为
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摘要
为开发环境友好型铋提取技术,在700℃下采用循环伏安、方波伏安和计时电位等方法研究了NaCl-KCl熔盐体系中Bi(Ⅲ)在玻碳电极上的电化学行为。在–0.3 V (vs. Ag/AgCl)电位下以玻碳电极为工作电极对NaCl-KCl-BiCl_3进行恒电位电解。结果表明,Bi(Ⅲ)在NaCl-KCl熔盐体系中的还原反应是一步得到3个电子的准可逆反应Bi3++3e-=Bi,起始还原电位为0.05 V (vs. Ag/AgCl),该反应受扩散控制。Berzins-Delahay方程和Sand方程计算的700℃下Bi(Ⅲ)在熔盐中的扩散系数分别为0.83×10~(–5)和1.0×10~(–5) cm~2/s。阴极产物为致密纯金属Bi,不含杂质。
Bismuth has a wide range of applications such as in metallurgy, chemical engineering, electronic industry, medical service, aeronautics, astronautics, and nuclear industry, etc., owing to its excellent properties including large density, low melting point, nontoxicity as well as the abnormal nature of expansion in cooling down and contraction in heating up. As one of the nonrenewable20 kVand scarce metal resources, the extraction and recycling of bismuth has received increasing attention in recent years. Molten salt electrolysis is one of the most widely used methods for metal extraction. Therefore, extraction of bismuth from BiCl_3 directly by molten salt electrolysis was evaluated in the present work in order to develop an environmentally friendly technology for bismuth recovery. Firstly, the electrochemical behavior of Bi(III) ions in molten NaCl-KCl at 700 ℃ was investigated by cyclic voltammetry, square wavevoltammetry, and chronopotentiometry on a glassy carbon working electrode. The results indicated that the reduction of Bi(III) in the NaCl-KCl molten salt was a one-step process with three electrons exchanged Bi~(3+)+3 e~-=Bi, and the initial reduction potential of Bi(III) ions was detected at 0.05 V(vs. Ag/AgCl), approximately. Meanwhile, the reduction of Bi(III) ions in the melts was a quasi-reversible diffusion-controlled process, and the diffusion coefficient of Bi(III) in molten –salt at 700 ℃ were determined to be 0.83×10~(-5) and 1.0× 10~(-5) cm~2/s, respectively, based on the results of cyclic voltammetry and chronopotentiometry using the Berzins-Delahay equation and the Sand equation. Then, potentiostatic electrolysis at –0.3 V(vs. Ag/AgCl) was carried out in molten NaCl-KCl-BiCl_3 under 700 ℃ and spherical metal granules were obtained around cathode. The cathodic products were compact in microstructure and confirmed to be pure bismuth with no other impurities detected by XRD and SEM-EDS analyses. The present results confirmed that it was an effective method for extraction of bismuth by direct electrolysis of bismuth chloride in molten NaCl-KCl, which could be subsequently used to recycling of bismuth from bismuth-bearing materials.
Bismuth has a wide range of applications such as in metallurgy, chemical engineering, electronic industry, medical service, aeronautics, astronautics, and nuclear industry, etc., owing to its excellent properties including large density, low melting point, nontoxicity as well as the abnormal nature of expansion in cooling down and contraction in heating up. As one of the nonrenewable20 kVand scarce metal resources, the extraction and recycling of bismuth has received increasing attention in recent years. Molten salt electrolysis is one of the most widely used methods for metal extraction. Therefore, extraction of bismuth from BiCl_3 directly by molten salt electrolysis was evaluated in the present work in order to develop an environmentally friendly technology for bismuth recovery. Firstly, the electrochemical behavior of Bi(III) ions in molten NaCl-KCl at 700 ℃ was investigated by cyclic voltammetry, square wavevoltammetry, and chronopotentiometry on a glassy carbon working electrode. The results indicated that the reduction of Bi(III) in the NaCl-KCl molten salt was a one-step process with three electrons exchanged Bi~(3+)+3 e~-=Bi, and the initial reduction potential of Bi(III) ions was detected at 0.05 V(vs. Ag/AgCl), approximately. Meanwhile, the reduction of Bi(III) ions in the melts was a quasi-reversible diffusion-controlled process, and the diffusion coefficient of Bi(III) in molten –salt at 700 ℃ were determined to be 0.83×10~(-5) and 1.0× 10~(-5) cm~2/s, respectively, based on the results of cyclic voltammetry and chronopotentiometry using the Berzins-Delahay equation and the Sand equation. Then, potentiostatic electrolysis at –0.3 V(vs. Ag/AgCl) was carried out in molten NaCl-KCl-BiCl_3 under 700 ℃ and spherical metal granules were obtained around cathode. The cathodic products were compact in microstructure and confirmed to be pure bismuth with no other impurities detected by XRD and SEM-EDS analyses. The present results confirmed that it was an effective method for extraction of bismuth by direct electrolysis of bismuth chloride in molten NaCl-KCl, which could be subsequently used to recycling of bismuth from bismuth-bearing materials.
引文
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[17]赵灿锋.Dy(III)在氯化物熔盐体系中欠电位沉积和氯化作用的研究及制备镁铝镝合金[D].哈尔滨:哈尔滨工程大学,2013:29-30.Zhao C F.Underpotential deposition and chlorination of Dy(III)in chloride molten salt system and electrodeposition of Mg-Al-Dy alloy[D].Harbin:Harbin Engineering University,2013:29-30.
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[19]Vandarkuzhali S,Gogoi N,Ghosh S,et al.Electrochemical behaviour of LaCl3 at tungsten and aluminium cathodes in LiClKCl eutectic melt[J].Electrochimica Acta,2012,59:245-255.
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[24]Tang H,Pesic B.Electrochemical behavior of LaCl3 and morphology of La deposit on molybdenum substrate in molten LiCl-KCl eutectic salt[J].Electrochimica Acta,2014,119:120-130.
[25]Vandarkuzhali S,Chandra M,Ghosh S,et al.Investigation on the electrochemical behavior of neodymium chloride at W,Al and Cd electrodes in molten LiCl-KCl eutectic[J].Electrochimica Acta,2014,145:86-98.
[26]Jia Y H,He H,Lin R H,et al.Electrochemical behavior of cerium(III)in NaCl-KCl molten salt[J].Journal of Radioanalytical and Nuclear Chemistry,2015,303(3):1763-1770.
[27]Han W,Ji N,Li M,et al.Electrochemical formation of Al-Tb alloys from Tb4O7 fluorinated by AlF3 in NaCl-KCl melts[J].Acta Physico-Chimica Sinica,2016,32(10):2538-2544.
[28]蔡艳青,刘红霞,许茜,等.铜在LiCl-KCl熔盐中的电化学行为研究[J].有色金属(冶炼部分),2015,(8):1-5.Cai Y Q,Liu H X,Xu Q,et al.Electrochemical behavior of copper in eutectic LiCl-KCl melt[J].Nonferrous Metals(Extractive Metallurgy),2015,(8):1-5.
[29]Bard A J,Faulkner L R.Electrochemical methods:fundamentals and applications[M].Beijing:Chemical Industry Press,2005:65-175.
[30]陈丽军,张密林,韩伟,等.Mn(II)在LiCl-KCl-MgCl2-MnCl2熔盐体系中的电化学行为[J].高等学校化学学报,2012,33(2):327-330.Chen L J,Zhang M L,Han W,et al.Electrochemical behavior of Mn(II)in the melt LiCl-KCl-MgCl2-MnCl2[J].Chemical Journal of Chinese Universities,2012,33(2):327-330.
[31]刘威,肖赛君,王振.NaCl-KCl熔盐体系中Cr(II)在W电极上的电化学行为[J].过程工程学报,2017,17(1):119-122.Liu W,Xiao S J,Wang Z.Electrochemical behavior of Cr(II)ion in NaCl-KCl melt at W electrode[J].The Chinese Journal of Process Engineering,2017,17(1):119-122.
[2]Chaus A S.Application of bismuth for solidification structure refinement and properties enhancement in as-cast high-speed steels[J].ISIJ International,2005,45(9):1297-1306.
[3]Cesarino I,Gouveia-Caridade C,Pauliukait?R,et al.Characterization and application of bismuth-film modified graphite-polyurethane composite electrodes[J].Electroanalysis,2010,22(13):1437-1445.
[4]Mamur H,Bhuiyan M R A,Korkmaz F,et al.A review on bismuth telluride(Bi2Te3)nanostructure for thermoelectric applications[J].Renewable and Sustainable Energy Reviews,2018,82(3):4159-4169.
[5]Bagwasi S,Tian B,Zhang J,et al.Synthesis,characterization and application of bismuth and boron co-doped Ti O2:a visible light active photocatalyst[J].Chemical Engineering Journal,2013,217(2):108-118.
[6]汪立果.铋冶金[M].北京:冶金工业出版社,1986:7-14.Wang L G.Bismuth metallurgy[M].Beijing:Metallurgical Industry Press,1986:7-14.
[7]Chen Y,Liao T,Li G,et al.Recovery of bismuth and arsenic from copper smelter flue dusts after copper and zinc extraction[J].Minerals Engineering,2012,39(12):23-28.
[8]Kim D,Wang S.Bismuth recovery from hydrochloric acid solution[J].Canadian Metallurgical Quarterly,2008,47(3):317-326.
[9]FiceriováJ,Balá?P,Villachica C L.Thiosulfate leaching of silver,gold and bismuth from a complex sulfide concentrates[J].Hydrometallurgy,2005,77(1/2):35-39.
[10]Castrillejo Y,Haarberg G M,Palmero S,et al.Chemical and electrochemical behaviour of BiCl3 in a PbCl2+KCl equimolar mixture at 475℃[J].Journal of Electroanalytical Chemistry,1994,373(1/2):149-155.
[11]Yang J G,He D W,Tang C B,et al.Thermodynamics calculation and experimental study on separation of bismuth from a bismuth glance concentrate through a low-temperature molten salt smelting process[J].Metallurgical and Materials Transactions B,2011,42(4):730-737.
[12]Ebe H,Ueda M,Ohtsuka T.Electrodeposition of Sb,Bi,Te,and their alloys in AlCl3-NaCl-KCl molten salt[J].Electrochimica Acta,2007,53(1):100-105.
[13]Ueda M,Tsuchiya S,Ohtsuka T.Electrodeposition of Bi-Sb-Te alloys by pulse electrolysis in AlCl3-NaCl-KCl molten salt[J].Electrochemistry,2009,77(8):659-662.
[14]Hua Z S,Wang J,Wang L,et al.Selective extraction of rare earth elements from NdFeB scrap by molten chlorides[J].ACSSustainable Chemistry&Engineering,2014,2(11):2536-2543.
[15]Hua Z S,Wang L,Wang J,et al.Extraction of rare earth elements from NdFeB scrap by AlF3-NaF melts[J].Materials Science and Technology,2015,31(8):1007-1010.
[16]Hua Z S,Liu H,Wang J,et al.Electrochemical behavior of neodymium and formation of Mg-Nd alloys in molten chlorides[J].ACS Sustainable Chemistry&Engineering,2017,5(9):8089-8096.
[17]赵灿锋.Dy(III)在氯化物熔盐体系中欠电位沉积和氯化作用的研究及制备镁铝镝合金[D].哈尔滨:哈尔滨工程大学,2013:29-30.Zhao C F.Underpotential deposition and chlorination of Dy(III)in chloride molten salt system and electrodeposition of Mg-Al-Dy alloy[D].Harbin:Harbin Engineering University,2013:29-30.
[18]Xiao S,Liu W,Gao L.Cathodic process of manganese(II)in NaCl-KCl melt[J].Ionics,2016,22(12):2387-2390.
[19]Vandarkuzhali S,Gogoi N,Ghosh S,et al.Electrochemical behaviour of LaCl3 at tungsten and aluminium cathodes in LiClKCl eutectic melt[J].Electrochimica Acta,2012,59:245-255.
[20]Li M,Liu B,Ji N,et al.Electrochemical extracting variable valence ytterbium from LiCl-KCl-YbCl3 melt on Cu electrode[J].Electrochimica Acta,2016,193:54-62.
[21]Wang C,Yi L,Hu H E,et al.Electrochemical behavior of cerium ion in molten LiCl-KCl[J].Journal of Rare Earths,2013,31(4):405-409.
[22]Wang Q,Wang Y,Liu H,et al.Electrochemical behavior of Bi(III)on a molybdenum electrode in NaCl-KCl eutectic molten salt[J].RSC Advances,2016,6(61):55953-55960.
[23]Bard A J,Faulkner L R.Electrochemical methods:fundamentals and applications[M].Beijing:Chemical Industry Press,2005:225-227.
[24]Tang H,Pesic B.Electrochemical behavior of LaCl3 and morphology of La deposit on molybdenum substrate in molten LiCl-KCl eutectic salt[J].Electrochimica Acta,2014,119:120-130.
[25]Vandarkuzhali S,Chandra M,Ghosh S,et al.Investigation on the electrochemical behavior of neodymium chloride at W,Al and Cd electrodes in molten LiCl-KCl eutectic[J].Electrochimica Acta,2014,145:86-98.
[26]Jia Y H,He H,Lin R H,et al.Electrochemical behavior of cerium(III)in NaCl-KCl molten salt[J].Journal of Radioanalytical and Nuclear Chemistry,2015,303(3):1763-1770.
[27]Han W,Ji N,Li M,et al.Electrochemical formation of Al-Tb alloys from Tb4O7 fluorinated by AlF3 in NaCl-KCl melts[J].Acta Physico-Chimica Sinica,2016,32(10):2538-2544.
[28]蔡艳青,刘红霞,许茜,等.铜在LiCl-KCl熔盐中的电化学行为研究[J].有色金属(冶炼部分),2015,(8):1-5.Cai Y Q,Liu H X,Xu Q,et al.Electrochemical behavior of copper in eutectic LiCl-KCl melt[J].Nonferrous Metals(Extractive Metallurgy),2015,(8):1-5.
[29]Bard A J,Faulkner L R.Electrochemical methods:fundamentals and applications[M].Beijing:Chemical Industry Press,2005:65-175.
[30]陈丽军,张密林,韩伟,等.Mn(II)在LiCl-KCl-MgCl2-MnCl2熔盐体系中的电化学行为[J].高等学校化学学报,2012,33(2):327-330.Chen L J,Zhang M L,Han W,et al.Electrochemical behavior of Mn(II)in the melt LiCl-KCl-MgCl2-MnCl2[J].Chemical Journal of Chinese Universities,2012,33(2):327-330.
[31]刘威,肖赛君,王振.NaCl-KCl熔盐体系中Cr(II)在W电极上的电化学行为[J].过程工程学报,2017,17(1):119-122.Liu W,Xiao S J,Wang Z.Electrochemical behavior of Cr(II)ion in NaCl-KCl melt at W electrode[J].The Chinese Journal of Process Engineering,2017,17(1):119-122.
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