A Review and Perspective on Analytical Methods of Critical Metal Elements
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摘要: 以稀有、稀散、稀土、铂族元素为主体的战略性关键金属矿产资源,在新材料、新能源和信息技术等新兴产业中发挥着越来越关键的作用。随着我国关键矿产资源地质调查的不断深入,关键金属元素以其赋存基体复杂、不同矿物含量差异大、化学性质不稳定等特点对分析测试技术提出了新的挑战。本文根据化学组成不同,对关键金属元素主要赋存基体进行了分类,主要分为硅酸盐、碳酸盐、硫酸盐、钨酸盐、磷酸盐、氧化物、硫化物、卤化物等。对于不同的基体岩石矿物,通常采用酸溶法(硝酸-氢氟酸组合、王水)或碱熔法等传统溶样方法进行化学消解。评述了当前关键金属元素测试常用的电子探针、电感耦合等离子体质谱、电感耦合等离子体发射光谱、X射线荧光光谱等仪器的特点及应用,总结了关键金属元素分析过程中出现的样品难溶解、回收率不完全、测试过程氧化物和同质异位素干扰、样品和标准基体不一致等常见问题,并提出了相应的解决方案。微区原位分析凭借其高效率、低成本、高空间分辨率的优势,以及野外现场分析凭借其简单快速、贴近野外工作的特点是关键金属元素测试技术发展的主要趋势。Abstract:
BACKGROUND Strategic critical metal mineral resources including rare, dispersed, rare earth and platinum group elements play an increasingly critical role in emerging industries such as new materials, new energy and information technology. With the deepening of the geological survey of key mineral resources in China, the critical metal elements present new challenges to analytical techniques due to their complex matrix, large differences in different mineral contents, and unstable chemical properties. OBJECTIVES To introduce recent analytical techniques and applications for critical metal elements in different types of geological samples. METHODS Based on different chemical composition, the main matrices of critical metal elements were classified, mainly divided into silicate, carbonate, sulfate, tungstate, phosphate, oxide, sulfide and halide. For different types of rocks and minerals, chemical digestion was largely carried out by traditional dissolution methods such as the acid dissolution method (nitric acid-hydrofluoric acid combination, aqua regia) or alkali fusion methods. RESULTS The characteristics and application of commonly used instruments including electronic probe microanalyzer, inductively coupled plasma-mass spectrometry, inductively coupled plasma-optical emission spectroscopy, and X-ray fluorescence spectroscopy were reviewed. The problems during critical metal analysis including incomplete dissolution, low recovery, oxides and isobaric interference, inconsistency between samples and standard matrices were reviewed and corresponding solutions were proposed. CONCLUSIONS In situ microanalysis with the advantages of high efficiency, low cost, and high spatial resolution, and field on-site geoanalysis with its simple, fast and close to field work features are the main trends in the development of critical metal elements analytical techniques. -
表 1 关键金属元素类别
Table 1. Categories of critical metal elements
金属类别 金属元素 稀有金属 锂(Li),铍(Be),铌(Nb),钽(Ta),锆(Zr),锶(Sr),
铷(Rb),铯(Cs)稀土金属 镧(La),铈(Ce),镨(Pr),钕(Nd),钷(Pm),
钐(Sm),铕(Eu),钆(Gd),铽(Tb),镝(Dy),
钬(Ho),铒(Er),铥(Tm),镱(Yb),镥(Lu),钇(Y)稀散金属 钪(Sc),锗(Ge),镓(Ga),铟(In),铊(Tl),铪(Hf),
铼(Re),镉(Cd),硒(Se),碲(Te)铂族金属 铂(Pt),铑(Rh),钯(Pt),锇(Os),铱(Ir),钌(Ru) 有色金属 锑(Sb),钨(W),锡(Sn),铋(Bi),钴(Co),钒(V),
钛(Ti)表 2 我国常见关键金属矿石矿物分类及消解方法
Table 2. Classification and dissolution methods of critical metal ores in China
赋存基体类型 赋存基体示例 所含关键金属元素 样品处理方法 矿床实例 单质 硫 Se 升华法 台湾龟山岛 硅酸盐 锂辉石 Li 酸溶法(硝酸-氢氟酸) 四川甲基卡 碳酸盐 火成碳酸岩 稀土元素,Zr,Hf,Nb,Ta 酸溶法(硝酸-氢氟酸) 湖北庙垭 硫酸盐 天青石、重晶石 Sr 碳酸钠置换法 重庆干沟 磷酸盐 磷块岩 稀土元素,U,Se 酸溶法(硝酸-氢氟酸) 贵州织金 钨酸盐 黑钨矿 Sc 酸溶法(硝酸-氢氟酸) 江西西华山 氧化物 铝土矿 Li,Sc,Nb,Ta 碱熔法 广西平果 硫化物 闪锌矿 Ge,In,Cd 酸溶法(硝酸-盐酸) 云南会泽 卤化物 卤水 Li,Rb,Cs,B 直接稀释法 西藏扎布耶 有机质 煤 Ge,Tl 酸溶法(硝酸-过氧化氢-氢氟酸) 云南临沧 -
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