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<p>Germanium purification faces significant challenges in removing refractory impurities (Al, Si, B, P) due to their segregation coefficients close to one and the presence of stable oxides during conventional zone refining, leading to low efficiency and extended processing cycles. To address these limitations, this study introduces an innovative two-stage processing technology that integrates alloying smelting with zone refining, leveraging thermodynamic-driven phase transformation and density-driven segregation. Iron (Fe) and calcium oxide (CaO) were strategically selected to form stable compounds (<i>e.g.</i>, Fe–Si alloy, Fe–B alloy, and Ca–Al–Si oxides), enabling efficient mechanical separation of refractory impurities. Alloying smelting (1300&#xa0;°C, 3 hours) with 1000 ppm Fe and 500 ppm CaO achieved mechanical removal of 99.41&#xa0;pct Si and 68.75 pct P through density-driven segregation. Subsequent zone refining (40 mm/hour, 3 cycles) further reduced Fe, Ca, Al, and B to 15.23, 5, 10, and 1.62 ppm, achieving removal rates of 97.46, 93.15, 84.24, and 93.48 pct, respectively. This integrated approach overcomes the inefficiency of traditional zone refining and establishes a scalable framework applicable to other metals facing similar challenges.</p> Graphical Abstract <p></p>

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A Novel Method for Purifying Germanium: Integrating Impurity Alloying with Zone Refining Processes

  • 期刊论文

  • 发表日期：

    2025年7月14日

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  • Zhu Huang,
  • Zhipeng Xu,
  • Xueyi Guo,
  • Qinghua Tian

摘要

Germanium purification faces significant challenges in removing refractory impurities (Al, Si, B, P) due to their segregation coefficients close to one and the presence of stable oxides during conventional zone refining, leading to low efficiency and extended processing cycles. To address these limitations, this study introduces an innovative two-stage processing technology that integrates alloying smelting with zone refining, leveraging thermodynamic-driven phase transformation and density-driven segregation. Iron (Fe) and calcium oxide (CaO) were strategically selected to form stable compounds (e.g., Fe–Si alloy, Fe–B alloy, and Ca–Al–Si oxides), enabling efficient mechanical separation of refractory impurities. Alloying smelting (1300 °C, 3 hours) with 1000 ppm Fe and 500 ppm CaO achieved mechanical removal of 99.41 pct Si and 68.75 pct P through density-driven segregation. Subsequent zone refining (40 mm/hour, 3 cycles) further reduced Fe, Ca, Al, and B to 15.23, 5, 10, and 1.62 ppm, achieving removal rates of 97.46, 93.15, 84.24, and 93.48 pct, respectively. This integrated approach overcomes the inefficiency of traditional zone refining and establishes a scalable framework applicable to other metals facing similar challenges.

Graphical Abstract