Regulating CaSi2 in High-Calcium Metallurgical-Grade Silicon via Aluminum Incorporation

Lei Zhou, Kuixian Wei, Kuisong Zhu, Junxi Nie, Xiaocong Deng, Wenhui Ma
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Abstract

The production of organic silicon (Si) monomer from metallurgical-grade silicon (MG–Si) is hindered by CaSi2, leading to a decreased yield of (CH3)2SiCl2. Therefore, strict control of CaSi2 content is essential. However, the existing MG–Si oxidation refining process fails to prevent the precipitation of FeSi2 and the reduction of Si8Al6Fe4Ca content, while simultaneously decreasing CaSi2 content. To address this issue, a novel method of adjusting aluminum (Al) content in MG–Si to reduce CaSi2 content and increase Si2Al2Ca or Si8Al6Fe4Ca content was proposed. The results indicated that the impurity ratio in MG–Si directly influenced the type of precipitating intermetallics. Specifically, when m(Al/Ca) < 1.35, CaSi2, FeSi2, and Si2Al2Ca were present. When 1.35 < m(Al/Ca) < 1.35 + 0.48 m(Fe/Ca), FeSi2, Si2Al2Ca, and Si8Al6Fe4Ca were encountered. Additionally, when the Al content m(Al/Ca) > 1.35 + 0.48 m(Fe/Ca), only Si2Al2Ca and Si8Al6Fe4Ca were observed. Upon adjusting the Al content in high-Ca MG–Si to m(Al/Ca) > 1.35, CaSi2 was effectively eliminated. Furthermore, within the experimental range, the average content of Si8Al6Fe4Ca precipitates increased from 12.84 to 37.94 wt pct after adjusting the Al content in the melt, representing a maximum increase of ~ 2.95 times. This study successfully elucidated the regulation of calcium (Ca)-containing intermetallics in high-Ca MG–Si, paving the way for the production of high-quality MG–Si raw materials for silicone monomer synthesis.

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通过掺铝调节高钙冶金级硅中的 CaSi2
从冶金级硅 (MG-Si) 中生产有机硅 (Si) 单体会受到 CaSi2 的阻碍,导致 (CH3)2SiCl2 的产量下降。因此,严格控制 CaSi2 的含量至关重要。然而,现有的 MG-Si 氧化精炼工艺无法在降低 CaSi2 含量的同时防止 FeSi2 的沉淀和 Si8Al6Fe4Ca 含量的降低。针对这一问题,提出了一种调整 MG-Si 中铝(Al)含量的新方法,以降低 CaSi2 含量,增加 Si2Al2Ca 或 Si8Al6Fe4Ca 含量。结果表明,MG-Si 中的杂质比例直接影响析出金属间化合物的类型。具体来说,当 m(Al/Ca) < 1.35 时,会出现 CaSi2、FeSi2 和 Si2Al2Ca。当 1.35 < m(Al/Ca) < 1.35 + 0.48 m(Fe/Ca) 时,出现了 FeSi2、Si2Al2Ca 和 Si8Al6Fe4Ca。此外,当铝含量 m(Al/Ca) > 1.35 + 0.48 m(Fe/Ca)时,只观察到 Si2Al2Ca 和 Si8Al6Fe4Ca。将高钙 MG-Si 中的铝含量调整到 m(Al/Ca) > 1.35 后,CaSi2 被有效消除。此外,在实验范围内,调整熔体中的铝含量后,Si8Al6Fe4Ca 沉淀的平均含量从 12.84 wt pct 增加到 37.94 wt pct,最大增幅约为 2.95 倍。这项研究成功地阐明了高钙 MG-Si 中含钙金属间化合物的调控,为生产用于合成有机硅单体的高质量 MG-Si 原料铺平了道路。
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