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    废硅提纯与回收利用研究现状及发展趋势

    Current Status and Future Trends in Recycling and Purifying Silicon Waste

    • 摘要: 随着光伏与半导体产业的持续扩张,高纯硅需求不断攀升,而硅片切割、工业硅冶炼及组件退役过程中产生的大量废硅资源则亟待高效回收与再利用。综合分析了光伏切割废料(SCW)、冶炼副产渣(MGSRS)及退役光伏组件(EoL-PV)的组成特征及杂质分布规律,系统综述了其在冶金级硅、光伏级硅、电子级硅、硅化物、有机硅化工及功能化硅材料等方面的研究进展。重点讨论了酸浸、熔渣精炼、真空精炼、区熔、等离子体处理、微波强化及电子束熔炼等技术的作用机理、工艺要点与应用效果。前人研究表明,废硅在降低能耗与碳排放、减少固废堆存和替代原生硅方面展现出显著优势,但仍存在成分波动、深度提纯难度大及产业化体系不完善等问题。未来研究应聚焦杂质去除与相变机理,构建多工艺协同及多废协同的集成流程,并推动标准规范与政策体系的建立,以实现废硅资源化利用的规模化、绿色化与高值化发展。

       

      Abstract: The rapid growth of the photovoltaic and semiconductor industries has dramatically increased the demand for high-purity silicon while generating large amounts of silicon waste during wafer slicing, metallurgical refining, and module decommissioning. Efficient recycling of waste silicon can mitigate environmental pressure and provide a sustainable raw material source for silicon-based industries. This work systematically reviews the purification, recovery, and reuse technologies of waste silicon, focusing on three major categories: silicon cutting waste (SCW), metallurgical-grade silicon refining slag (MGSRS), and end-of-life photovoltaic modules (EoL-PV). The physicochemical characteristics of these wastes, including phase composition, impurity distribution, and structural morphology, are analyzed to establish the relationship between their origins and corresponding purification strategies. Experimental and industrial results reported in recent literature are compared to identify the optimal parameters for impurity removal. For SCW, acid leaching with HF-HCl or HNO3-HF mixtures achieved Fe, Al, and Ca removal efficiencies exceeding 95% under temperatures of 50–60 ℃ and moderate acid concentrations. In MGSRS refining, CaO-SiO2-Al2O3 or Fe2O3-SiO2-based slags effectively removed Ti, C, and Ca impurities through oxidation and selective slagging reactions, yielding silicon purities above 99.8%. Vacuum refining and zone melting remove volatile impurities (e.g., P) and metallic impurities, respectively; however, removing B remains a challenge due to its segregation coefficient being close to unity. Emerging physical purification methods, including plasma, microwave, and electron-beam treatments, are discussed in terms of heat transfer behavior, impurity volatilization kinetics, and energy consumption. The synergistic combination of chemical and physical refining routes has been shown to markedly improve purification efficiency, shorten processing time, and reduce reagent use. The thermodynamic feasibility and kinetic constraints of impurity reactions are summarized to provide theoretical guidance for multi-step integration. Regarding reutilization, purified silicon waste can be converted into metallurgical-grade, solar-grade, or electronic-grade silicon depending on purity requirements. In addition, secondary utilization pathways include the synthesis of SiC and Si3N4 ceramics, Si-C composite anodes for lithium-ion batteries, and porous silicon for energy storage and photothermal conversion. Life-cycle analyses indicate that recycling 1 t of silicon waste saves approximately 8–10 MW·h of energy and reduces CO2 emissions by more than 5 t compared with primary silicon production. Overall, waste silicon recycling offers substantial environmental and economic benefits, but large-scale industrial implementation is still limited by impurity variability, lack of standardized process control, and the high cost of deep purification. Future work should focus on elucidating the thermodynamic and kinetic mechanisms of impurity removal, optimizing multi-process coupling between refining and solidification, and developing modularized refining-functionalization systems. Establishing unified evaluation criteria and techno-economic models will be key to achieving sustainable, high-value recycling of waste silicon materials.

       

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