弱氧化剂CO_2(g)对含钒铁水吹炼制钒渣的影响
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摘要
采用弱氧化剂选择性氧化含钒铁水,先弱氧化脱硅,再强氧化提钒,以获得高品位的钒渣。对弱氧化剂CO_2浅度氧化含钒铁水炼制钒渣进行了理论分析,确定脱硅保钒反应的物理化学条件,研究了温度、CO_2气体流量、搅拌和熔剂等因素对脱硅保钒反应的影响及脱硅反应产物的分布。结果表明,温度1450℃及CO_2气体流量1 L/min、有搅拌条件下,脱硅率高达68.62%,而钒氧化率仅为0.73%。
75%~85% of vanadium products in the world are produced from the vanadium-titanium magnetite, in vanadium-titanium magnetite, Fe, V and Ti are distributed in the isomorphism phase, which cannot be enriched and separated by physical methods. Usually, the vanadium slag and the semi-steel are obtained by the oxygen blowing process in the steel making process. The semi-steel is used to produce steel, and the vanadium slag is the raw material for extracting vanadium. When vanadium slag is obtained by blowing vanadium-bearing molten iron with oxygen, the impurities such as Ca, Mg, Al, Ti and Si in the molten iron enter into slag phase along with V, oxygen as astrong oxidizer. Both vanadium oxide and impurity oxides are contained in the vanadium slag, resulting in high impurity content and low vanadium grade, which make the subsequent vanadium extraction process costly, that is the drawback of the current vanadium slag process. Weak oxidizer CO_2(g) was used in this research to produce the low-silicon and high-vanadium slag by selective oxidation, during which Si was removed into slag firstly and then V left in the molten iron by weak oxidation. Theoretical analysis was firstly performed and then the effects of temperature, flow rate of CO_2(g), stirring and smelt agent on the desilication process were investigated. The results showed that the desilication rate reached 68.62%, and the oxidation rate of vanadium was only 0.73% when the desilication process was performed with stirring and CO_2(g) flow rate of 1 L/min at 1 450℃.
75%~85% of vanadium products in the world are produced from the vanadium-titanium magnetite, in vanadium-titanium magnetite, Fe, V and Ti are distributed in the isomorphism phase, which cannot be enriched and separated by physical methods. Usually, the vanadium slag and the semi-steel are obtained by the oxygen blowing process in the steel making process. The semi-steel is used to produce steel, and the vanadium slag is the raw material for extracting vanadium. When vanadium slag is obtained by blowing vanadium-bearing molten iron with oxygen, the impurities such as Ca, Mg, Al, Ti and Si in the molten iron enter into slag phase along with V, oxygen as astrong oxidizer. Both vanadium oxide and impurity oxides are contained in the vanadium slag, resulting in high impurity content and low vanadium grade, which make the subsequent vanadium extraction process costly, that is the drawback of the current vanadium slag process. Weak oxidizer CO_2(g) was used in this research to produce the low-silicon and high-vanadium slag by selective oxidation, during which Si was removed into slag firstly and then V left in the molten iron by weak oxidation. Theoretical analysis was firstly performed and then the effects of temperature, flow rate of CO_2(g), stirring and smelt agent on the desilication process were investigated. The results showed that the desilication rate reached 68.62%, and the oxidation rate of vanadium was only 0.73% when the desilication process was performed with stirring and CO_2(g) flow rate of 1 L/min at 1 450℃.
引文
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[2]张生芹.钒渣体系物化性能及相平衡的研究[D].重庆:重庆大学,2012:5-40.Zhang S Q.Research on physicochemical properties and phase equilibrium of vanadium slag[D].Chongqing:Chongqing University,2012:5-40.
[3]张生芹,任正德,邓能运.Si O2对钒渣粘度的影响预测[J].中国稀土学报,2012,30(专辑):170-174.Zhang S Q,Ren Z D,Deng N Y.Research on forecast of SiO2 on vanadium slag viscosities[J].Journal of Chinese Society of Rare Earths,2012,30(Spec.Issue):170-174.
[4]黄正华.高硅铁水转炉提钒对钒渣质量的影响及对策[J].四川化工,2010,13(6):35-40.Huang Z H.The effect of high silicon molten iron used in converter V-recovering on the quality of vanadium slag and the countermeasure[J].Sichuan Chemical Engineering,2010,13(6):35-40.
[5]高剑辉.转炉提钒工艺对钒渣质量的影响[J].金属世界,2008,(4):1-3.Gao J H.The effect of vanadium extraction by converter process on the quality of vanadium slag[J].Metal World,2008,(4):1-3.
[6]陈东辉,杨树德.钒渣化学形成理论研究[J].河北冶金,1993,(5):31-39.
[7]工业和信息化部.《产业关键共性技术发展指南(2017)》[Z].2017-10-18.
[8]隋智通,娄太平,王明华.含钒硅铁水制备低硅钛型钒渣的方法:CN 201710363475.0[P].2017-05-22.
[9]霍首星,隋智通,娄文博,等.含钒硅铁水CO2脱硅保钒实验研究[J].材料与冶金学报,2016,15(3):166-170.Huo S X,Sui Z T,Lou W B,et al.Study on removal of silicon and keeping vanadium in hot metal containing vanadium and silicon with carbon dioxide injection[J].Journal of Materials and Metallurgy,2016,15(3):166-170.
[10]黄希祜.钢铁冶金原理,第3版[M].北京:冶金工业出版社,2002:46-440.Huang X H.Principle of iron and steel metallurgy,third Ed.[M].Beijing:Metallurgy Industrial Press,2002:46-440.
[11]Atkins P.Physical chemistry,8th Ed.[M].Oxford:Oxford University Press,1987:200-390.
[12]林洁,王新华,周荣章,等.含钒铁水预脱硅时硅与钒的分离[J].钢铁,1989,(6):14-19.
[13]张景宜.含钒铁水炼钢应用研究[J].河南冶金,2013,21(3):12-14.Zhang J Y.Research of smelting hot metal containing vanadium[J].Henan Metallurgy,2013,21(3):12-14.
[14]甄小鹏.转炉提钒过程中碳、钒氧化的热力学和宏观动力学研究[D].重庆:重庆大学,2012:4-20.Zhen X P.Thermodynamic and macro-kinetic studies on oxidations of carbon and vanadium during vanadium extraction by converter[D].Chongqing:Chongqing University,2012:4-20.
[15]梁英教,车荫昌.无机物热力学数据手册[M].沈阳:东北大学出版社,1994:449-485.
[16]孙迪.含钒铁水钛、钒氧化的热力学分析[D].包头:内蒙古科技大学,2014:3-15.Sun D.Thermodynamic analysis of titanium and vanadium oxidation in iron water[D].Baotou:Inner Mongolia University of Science&Technology,2014:3-15.
[17]Werme A,Astrom C.Recovery of vanadium from melt iron?thermodynamics and injection applications[J].Scandinavian Journal of Metallurgy,1986,15(6):273-278.
[18]李丹柯.含钒铁水钒氧化动力学研究[D].重庆:重庆大学,2009:3-15.Li D K.Study on oxidation kinetics of vanadium in hot metal containing vanadium[D].Chongqing:Chongqing University,2009:3-15.
[19]刘文权.低碳炼铁:钢铁业发展低碳经济的重点[N].世界金属导报,2010-05-11(046).
[20]朱荣,毕秀荣,吕明.CO2在炼钢工艺的应用及发展[J].钢铁,2012,47(3):1-5.Zhu R,Bi X R,LüM.Application and development of carbon dioxide in the steelmaking process[J].Iron&Steel,2012,47(3):1-5.
[21]魏寿昆.冶金过程热力学[M].上海:上海科学技术出版社,1980:10-20
[22]车荫昌.冶金热力学[M].沈阳:东北工学院出版社,1989:41-50.
[23]张廷安,刘燕,王东兴,等.氧气底吹造锍过程中气泡冶金行为的水模实验研究[C]//中国金属学会.第十五届冶金反应工程学会议论文集.2011:651-656.Zhang T A,Liu Y,Wang D X,et al.Experimental study of water model on bubble metallurgical behavior in oxygen bottom blown matte manufacturing[C]//The Chinse Society for Metals.The Fifteenth Symposium Collection of Metallurgical Reaction Engineering Society.2011:651-656.
[24]Hornby-Anderson S,Douglas C L,Bermel C L.Use of CO2 in the AOD[C]//Warrendale Iron and Steel Society.The 48th Electric Furnace Conference Proceedings.1990:297-304.
[25]文光远.含钒钛铁水的预处理[J].重庆大学学报,1999,22(2):113-120.Wen G Y.Pretreatment of the hot iron containing vanadium and titanium[J].Journal of Chongqing University,1999,22(2):113-120.