造渣-吹气联合精炼去除冶金硅中硼杂质的研究
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摘要
对比研究了分别采用SiO_2-CaO-CaCl_2三元渣系精炼和喷吹氩气搅拌的造渣-吹气联合精炼方法进行冶金硅精炼的除硼效果。分别探讨了造渣精炼热力学,精炼前后硅样表面形貌变化,以及造渣-吹气联合精炼过程中不同吹气位置对于除硼效果的影响。研究发现,精炼后硅样品中存在Si-Ca、Si-W-Ti等析出相,B、P等杂质富集在析出相中;经酸洗处理后,造渣精炼的除硼率为55.42%,造渣-吹气联合精炼的除硼率为62.32%,造渣-吹气联合精炼可以有效去除硅中硼杂质。
The boron removal effect of metallurqical silicon by using SiO_2-CaO-CaCl_2 ternary slag system refining and argon injection agitation combined slag-gas refining respectivery was studied. The thermodynamics of slag refining, the changes of surface morphology of silicon sample before and after refining, and the effect of different blowing positions on the boron removal in the process of slag-gas combined refining were discussed respectively. It is found that Si-Ca, Si-W-Ti and other precipitated phases exist in the refined silicon sample, and B, P and other impurities are enriched in the precipitated phase; after pickling, the boron removal rate of slag refining is 55.42% and the boron removal rate of slag-gas combined refining is 62.32%. The boron impurity in silicon can be effectively removed by slag-gas combined refining.
The boron removal effect of metallurqical silicon by using SiO_2-CaO-CaCl_2 ternary slag system refining and argon injection agitation combined slag-gas refining respectivery was studied. The thermodynamics of slag refining, the changes of surface morphology of silicon sample before and after refining, and the effect of different blowing positions on the boron removal in the process of slag-gas combined refining were discussed respectively. It is found that Si-Ca, Si-W-Ti and other precipitated phases exist in the refined silicon sample, and B, P and other impurities are enriched in the precipitated phase; after pickling, the boron removal rate of slag refining is 55.42% and the boron removal rate of slag-gas combined refining is 62.32%. The boron impurity in silicon can be effectively removed by slag-gas combined refining.
引文
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[2]Li Feng,Xing Pengfei,Li Dagang,et al.Removal of phosphorus from metallurgical grade silicon by Ar-H2O gas mixtures[J].Transactions of Nonferrous Metals Society of China,2013,23(11):3470-3475.
[3]Johnston M D,Barati M.Distribution of impurity elements in slag-silicon equilibria for oxidative refining of metallurgical silicon for solar cell applications[J].Solar Energy Materials&Solar Cells,2010,94(12):2085-2090.
[4]Johnston M D,Barati M.Effect of slag basicity and oxygen potential on the distribution of boron and phosphorus between slag and silicon[J].Journal of Non-Crystalline Solids,2011,357(3):970-975.
[5]Suzuki K,Sakaguchi K,Nakagiri T,et al.Gaseous removal of phosphorus and boron from molten silicon[J].Journal of the Japan Institute of Metals,1990,54:161-167.
[6]Visnovec K.Refining of silicon during its solidification from a Cu-Si melt[J].Master,2012,58(3):93-94.
[7]Wang Shengqian,Zhang Lifeng,Yang Shufeng,et al.Electromagnetic separation of nonmetallic inclusions from liquid steel by high frequency magnetic field[J].Journal of Iron&Steel Research,2012,10(S2):866-878.
[8]Dong A,Zhang Lifeng,Damoah L.Beneficial and technological analysis for the recycling of solar grade silicon wastes[J].JOM,2011,63(1):23-27.
[9]Khattak C P,Schmid F.Processing of MG silicon for photovoltaic applications[J].Proc.-Electrochem.Soc.,1983,83:5-11.
[10]Flamant G,Kurtcuoglu V,Murray J,et al.Purification of metallurgical grade silicon by a solar process[J].Solar Energy Materials&Solar Cells,2006,90(14):2099-2106.
[11]张立峰,李亚琼.太阳能级多晶硅的精炼方法[M].北京:冶金工业出版社,2017:20-21.
[12]Morita K,Miki T.Thermodynamics of solar-grade-silicon refining[J].Intermetallics,2003,11(11/12):1111-1117.
[13]Wu Jijun,Ma Wenhui,Yang Bin.Boron removal from metallurgical grade silicon by oxidizing refining[J].Chinese Journal of Nonferrous Metals,2009,19(2):463-467.
[14]Nishimoto H,Morita K.The rate of boron elimination from molten silicon by slag and Cl2gas treatment[M].John Wiley&Sons,Inc.,2011:701-708.
[15]Wu Jijun,Ma Wenhui,Li Yanlong,et al.Thermodynamic behavior and morphology of impurities in metallurgical grade silicon in process of O2blowing[J].Transactions of Nonferrous Metals Society of China,2013,23(1):260-265.
[16]Xia Zhenfei,Wu Jijun,Ma Wenhui,et al.Separation of boron from metallurgical grade silicon by a synthetic Ca O-Ca Cl2slag treatment and Ar-H2O-O2gas blowing refining technique[J].Separation&Purification Technology,2017,187:25-33.
[17]徐敏.冶金级硅炉外吹气-熔渣联合精炼除硼、磷的工艺研究[D].昆明:昆明理工大学,2016.
[18]Lu Chenghao,Huang Liuqing,Lai Huixian,et al.Effects of slag refining on boron removal from metallurgical-grade silicon using recycled slag with active component[J].Separation Science&Technology,2015,50(17):2759-2766.
[19]Ban Boyuan,Li Jingwei,Bai Xiaolong,et al.Mechanism of Bremoval by solvent refining of silicon in Al-Si melt with Ti addition[J].Journal of Alloys&Compounds,2016,672:489-496.
[20]Esfahani S,Barati M.Purification of metallurgical silicon using iron as an impurity getter part I:growth and separation of Si[J].Metals&Materials International,2011,17(5):823-829.
[21]张家芸,邢献然,宋波,等.冶金物理化学[M].北京:冶金工业出版社,2004:144-150.
[22]Ikeda T,Maeda M.Elimination of boron in molten silicon by reactive rotating plasma arc melting[J].Mater.Trans.Jim,2007,37(5):983-987.
[23]Nordstrand E,Tangstad M.Removal of boron from silicon by moist hydrogen gas[J].Metallurgical&Materials Transactions B,2012,43(4):814-822.
[24]Suzuki K,Kumagai T,Sano N.Removal of boron from metallurgical-grade silicon by applying the plasma treatment[J].ISIJ International,1992,32(5):630-634.
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