Si-Cu合金精炼与造渣精炼去除冶金级硅中金属杂质
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摘要
采用Si-Cu合金精炼与CaO-SiO_2-CaCl_2造渣精炼相结合的方法对冶金级硅进行精炼,通过多种分析方法考察了合金造渣过程、渣剂添加剂和合金成分对金属杂质Fe、Al和Ca去除效果的影响.结果表明,提高Si-Cu合金中Cu的质量分数可以有效增加Cu_3Si相在Si中的含量,造渣精炼过程会影响Si-Cu合金的相转变,造渣后金属杂质Fe和Ca聚集在Si-Cu合金的Cu_3Si相中.在渣剂中添加CaCl_2助溶剂可降低渣剂黏度以促进传质过程,从而有效提高金属杂质Fe、Al和Ca的去除率.此外,随着Si-Cu合金中Cu质量分数的增加,造渣后合金相中Cu的析出现象明显,Fe的去除率上升,Ca的去除率下降,而Al的去除率不变.当Si-30%Cu合金与CaO-SiO_2-CaCl_2(质量比9∶9∶2)渣剂进行精炼后,Fe、Al和Ca的去除率分别为68%,94%和86%.
A combined process of Si-Cu alloy refining and CaO-SiO_2-CaCl_2 slag refining was used to remove metallic impurities,Fe,Al and Ca,from metallurgical grade silicon(MG-Si).Effects of refining procedure,slag addition,and alloy composition on the removal efficiency were investigated using several methods.It was found that the content of the Cu_3 Si phase in the Cu-alloyed MG-Si increased when the mass fraction of Cu increased.The slag refining would affect the phase transformation of the Si-Cu alloy,and impurities,Fe and Ca,were found to concentrate in the Cu_3 Si phase after slag refining.The addition of CaCl_2 facilitated the mass transfer process by decreasing the viscosity of the slag,thus enhancing the removal efficiency of impurities,Fe,Al and Ca.With the mass fraction of Cu increasing,more Cu was precipitated after slag refining,the removal efficiency of Fe and Ca increased and reduced,respectively,while that of Al was unchanged.When Si-30%Cu alloy was refined with CaO-SiO_2-CaCl_2(9∶9∶2,by mass)slag,the removal efficiencies of Fe,Al and Ca were 68%,94%,and 86%,respectively.
A combined process of Si-Cu alloy refining and CaO-SiO_2-CaCl_2 slag refining was used to remove metallic impurities,Fe,Al and Ca,from metallurgical grade silicon(MG-Si).Effects of refining procedure,slag addition,and alloy composition on the removal efficiency were investigated using several methods.It was found that the content of the Cu_3 Si phase in the Cu-alloyed MG-Si increased when the mass fraction of Cu increased.The slag refining would affect the phase transformation of the Si-Cu alloy,and impurities,Fe and Ca,were found to concentrate in the Cu_3 Si phase after slag refining.The addition of CaCl_2 facilitated the mass transfer process by decreasing the viscosity of the slag,thus enhancing the removal efficiency of impurities,Fe,Al and Ca.With the mass fraction of Cu increasing,more Cu was precipitated after slag refining,the removal efficiency of Fe and Ca increased and reduced,respectively,while that of Al was unchanged.When Si-30%Cu alloy was refined with CaO-SiO_2-CaCl_2(9∶9∶2,by mass)slag,the removal efficiencies of Fe,Al and Ca were 68%,94%,and 86%,respectively.
引文
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[2]李亚琼,张立峰,马玉生,等.凝固精炼、造渣精炼提纯冶金硅的研究进展[J].功能材料,2017,48(3):3028-3034.
[3] SAFARIAN J,TRANELL G,TANGSTAD M.Boron removal from silicon by CaO-Na2O-SiO2ternary slag[J].Metallurgical and Materials Transactions E,2015,2(2):109-118.
[4] MARGARIDO F,MARTINS J P,FIGUEIREDO M O,et al.Kinetics of acid leaching refining of an industrial Fe-Si alloy[J].Hydrometallurgy,1993,34(1):1-11.
[5] GALGALI R K,MOHANTY B C,GUMASTE J L,et al.Studies on slag refining and directional solidification in the purification of silicon[J].Solar Energy Materials,1987,16(4):297-307.
[6] DELANNOY Y,ALEMANY C,LI K I,et al.Plasmarefining process to provide solar-grade silicon[J].Solar Energy Materials and Solar Cells,2002,72(1/2/3/4):69-75.
[7] JIANG D C,TAN Y,SHI S,et al.Removal of phosphorus in molten silicon by electron beam candle melting[J].Materials Letters,2012,78:4-7.
[8] KHAJAVI L T,MORITA K,YOSHIKAWA T,et al.Thermodynamics of boron distribution in solvent refining of silicon using ferrosilicon alloys[J].Journal of Alloys and Compounds,2015,619:634-638.
[9] YOSHIKAWA T,MORITA K.Refining of silicon during its solidification from a Si-Al melt[J].Journal of Crystal Growth,2009,311(3):776-779.
[10] MITRASINOVICA M,UTIGARD T A.Refining silicon for solar cell application by copper alloying[J].Silicon,2009,1(4):239-248.
[11] MA X D,YOSHIKAWA T,MORITA K.Si growth by directional solidification of Si-Sn alloys to produce solargrade Si[J].Journal of Crystal Growth,2013,377:192-196.
[12]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,2017:81-85.
[13] KEENE B J.A review of the surface tension of silicon and its binary alloys with reference to Marangoni flow[J].Surface and Interface Analysis,1987,10(8):367-383.
[14] HUANG L Q,LAI H X,GAN C H,et al.Separation of boron and phosphorus from Cu-alloyed metallurgical grade silicon by CaO-SiO2-CaCl2 slag treatment[J].Separation and Purification Technology,2016,170:408-416.
[15] OHSHIMA Y,YOSHIKAWA T,MORITA K.Effect of solidification conditions on Si growth for Si-Cu melts[C]∥Supplemental Proceedings:Materials Processing and Engery Materials.Hoboken:John Wiley&Sons,Inc.,2011:677-684.
[16] MA X,YOSHIKAWA T,MORITA K.Purification of metallurgical grade Si combining Si-Sn solvent refining with slag treatment[J].Separation and Purification Technology,2014,125:264-268.
[17] LI M,UTIGARD T,BARATI M.Removal of boron and phosphorus from silicon using CaO-SiO2-Na2O-Al2O3flux[J].Metallurgical and Materials Transactions B,2014,45(1):221-228.
[18]杜冰,王志,孙丽媛,等.复合熔析精炼去除工业硅中的非金属杂质硼[J].过程工程学报,2015,15(3):393-399.
[19] KRYSTAD E,JAKOBSSON L K,TANG K,et al.Thermodynamic behavior and mass transfer kinetics of boron between ferrosilicon and CaO-SiO2 slag[J].Metallurgical and Materials Transactions B,2017,48(5):2574-2582.
[20]曹盼盼,李佳艳,李亚琼,等.铝硅合金低温造渣精炼提纯冶金硅的研究[J].热加工工艺,2016,45(13):73-76,80.
[21] 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 NonCrystalline Solids,2011,357(3):970-975.
[22] PARK J H,MIN D J,SONG H S.The effect of CaF2on the viscosities and structures of CaO-SiO2(-MgO)-CaF2slags[J].Metallurgical and Materials Transactions B,2002,33(5):723-729.
[23] ALZAMANI M,JAFARZADEH K.The effect of preoxidation treatment on corrosion behavior of Ni-Cu-FeAl anode in molten CaCl2salt[J].Oxidation of Metals,2018,89(5/6):623-640.
[24] GUO H Z,CHEN Y Z,PING H M,et al.Facile synthesis of Cu and Cu@Cu-Ni nanocubes and nanowires in hydrophobic solution in the presence of nickel and chloride ions[J].Nanoscale,2013,5(6):2394-2402.
[25]徐俊杰,朱律均,齐航,等.Cu的腐蚀与缓蚀的光电化学研究[J].金属学报,2008,44(11),1360-1365.
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