电渣重熔用五元高氟渣高温挥发机制
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摘要
为探究高温过程电渣组元挥发机理,以电渣重熔用高氟渣CaF_2-CaO-SiO_2-Al_2O_3-MgO五元渣系为基础研究炉渣高温挥发机制,通过FactSage理论计算、热重及高温质谱检测,结合1 000～1 500℃高温焙烧试验以及XRF检测与SEM物相观察,对炉渣加热过程成分及物相变化进行了研究。结果表明,温度为550～800℃时,CaF_2与SiO_2反应生成SiF_4气体;温度为800～1 200℃时,CaF_2与MgO反应生成MgF_2气体,同时与少量Al_2O_3反应生成AlF_3气体;温度为1 200～1 500℃时,挥发分主要为CaF_2及少量AlF_3。在高温区(1 000～1 400℃),晶体主要为二铝酸钙和和少量枪晶石;当温度达到1 500℃,晶体主要为枪晶石结构,为探究高温过程电渣组元挥发机理以及电渣制备工艺的优化提供参考。
In order to explore the volatilization mechanism of the ESR slag component under high-temperatures,the high-temperature volatilization mechanism of slag is studied based on the CaF_2-CaO-SiO_2-Al_2O_3-MgO slag system for the Electroslag remelting(ESR)slag with a high fluoride.Using the calculation of FactSage software,thermogravimetric(TG)experiments and mass spectrometry(MS)analyses under a high temperature,combined with high-temperature roasting experiments,XRF analyses,SEM phase observations,the results have indicated:CaF_2 reacts with SiO_2 and MgO to form SiF_4 and MgF_2 gas between 550-800℃;CaF_2 reacts with MgO to form MgF_2 gas and reacts with a small amount of Al_2O_3 to form AlF_3 gas between 800-1 200℃;the volatile is mainly CaF_2 with a small amount of AlF_3 in the range of 1 200-1 500℃.The crystal is mainly calcium dialuminate and a small amount of cuspidine in the high temperature region(1 000-1 400 ℃),and when the temperature is increased to 1 500℃,the crystal is mainly cuspidine.The purpose is to explore the volatilization mechanism of the ESR slag component under high-temperatures which has reference value of the optimization of the ESR slag preparation process.
In order to explore the volatilization mechanism of the ESR slag component under high-temperatures,the high-temperature volatilization mechanism of slag is studied based on the CaF_2-CaO-SiO_2-Al_2O_3-MgO slag system for the Electroslag remelting(ESR)slag with a high fluoride.Using the calculation of FactSage software,thermogravimetric(TG)experiments and mass spectrometry(MS)analyses under a high temperature,combined with high-temperature roasting experiments,XRF analyses,SEM phase observations,the results have indicated:CaF_2 reacts with SiO_2 and MgO to form SiF_4 and MgF_2 gas between 550-800℃;CaF_2 reacts with MgO to form MgF_2 gas and reacts with a small amount of Al_2O_3 to form AlF_3 gas between 800-1 200℃;the volatile is mainly CaF_2 with a small amount of AlF_3 in the range of 1 200-1 500℃.The crystal is mainly calcium dialuminate and a small amount of cuspidine in the high temperature region(1 000-1 400 ℃),and when the temperature is increased to 1 500℃,the crystal is mainly cuspidine.The purpose is to explore the volatilization mechanism of the ESR slag component under high-temperatures which has reference value of the optimization of the ESR slag preparation process.
引文
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[4]危亚军,郭显胜,黄永钢,等.80t低频气保恒熔速电渣炉的技术特点及应用[J].中国冶金,2017,27(6):58.(WEI Yajun,GUO Xian-sheng,HUANG Yong-gang,et al.Technical feature and application of 80tESR furnace with low-frequency,gas protection and constant melting rate[J].China Metallurgy,2017,27(6):58.)
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[6]赵俊学,尚南,赵忠宇,等.电渣重熔用中氟渣配渣方式对熔点测定的影响[J].钢铁,2018,53(8):44.(ZHAO Jun-xue,SHANG Nan,ZHAO Zhong-yu,et al.Influence of slag preparation mode on melting point of ESR slag with medium fluoride content[J].Iron and Steel,2018,53(8):44.)
[7]李正邦.电渣冶金的理论与实践[M].北京:冶金工业出版社,2010.(LI Zheng-bang.Electroslag Metallurgy Theory and Practice[M].Beijing:Metallurgical Industry Press,2010.)
[8]张晨,刘世洲,王文忠.CaO-SiO2-CaF2三元渣系的挥发率[J].钢铁研究学报,1998,10(6):16.(ZHANG Chen,LIU Shi-zhou,WANG Wen-zhong.Volatility of ternary flux CaOSiO2-CaF2[J].Journal of Iron and Steel Research,1998,10(6):16.)
[9]苗志奇,成国光,李世健,等.工业电渣重熔过程电极插入深度数学模型及应用[J].钢铁,2018,53(9):25.(MIAO Zhiqi,CHENG Guo-guang,LI Shi-jian,et al.Mathematical model of electrode immersing depth in industrial electroslag remelting process and application[J].Iron and Steel,2018,53(9):25.)
[10]陈艳梅,赵俊学,路晓涛,等.CaF2渣系失重与成分变化的试验研究[J].钢铁研究学报,2010,22(12):11.(CHEN Yanmei,ZHAO Jun-xue,LU Xiao-tao,et al.Experimental study on weight loss and compositional variations of slag system bearing bearing CaF2[J].Journal of Iron and Steel Research,2010,22(12):11.)
[11]巨建涛,吕振林,焦志远,等.CaF2-SiO2-CaO渣系的非等温挥发行为[J].过程工程学报,2012,12(4):618.(JU Jiantao,LZhen-Lin,JIAO Zhi-yuan,et al.Non-isothermal analysis on the evaporation behavior of CaF2-SiO2-CaO system slag[J].The Chinese Journal of Process Engineering,2012,12(4):618.)
[12]郭子亮,崔雅茹,赵俊学,等.高铅渣物理化学性能测定的偏差规律[J].辽宁科技大学学报,2016,39(1):47.(GUO Ziliang,CUI Ya-ru,ZHAO Jun-xue,et al.Deviation prediction on physicochemical properties of high-lead slag[J].Journal of university of Science and Technology Liaoning,2016,39(1):47.)
[13]庄迎,李吉东.GA-BP渣系活度预测模型及不锈钢脱氧机理[J].中国冶金,2017,27(1):7.(ZHUANG Ying,LI Jidong.Prediction model of GA-BP molten slag activity and deoxidation mechanism of stainless steel[J].China Metallurgy,2017,27(1):7.)
[14]陈艳梅,赵俊学.电渣冶金过程炉渣成分变化及其影响研究[J].工业加热,2014,43(3):23.(CHEN Yan-mei,ZHAO Jun-xue.Study on slag chemical composition change and its influence during ESR process[J].Industrial Heating,2014,43(3):23.)
[15]郭仲文,王翠香.含CaF2熔渣体系挥发率测定的研究[J],东北工学院学报,1987,52(3):381.(GUO Zhong-wen,WANG Cui-xiang.Study on the volatility measurement for CaF2-cotaining slag systems[J].Journal of Northeastern Polytechnical College,1987,52(3):381.)
[2]陈艳梅,赵俊学,樊军,等.电渣重熔过程中渣成分变化的研究[J].特殊钢,2010,31(6):7.(CHEN Yan-mei,ZHAO Jun-xue,FAN Jun,et al.A study on variations of slag ingredient during electroslag remelting proces[J].Special Process,2010,31(6):7.)
[3]赵俊学,葛蓓蕾,崔雅茹.含易挥发组元炉渣的高温性能检测[J].工业加热,2016,45(2):12.(ZHAO Jun-xue,GE Beilei,CUI Ya-ru,et al.High temperature properties measurement of slag with higher volatile content[J].Industrial Heating,2016,45(2):12.)
[4]危亚军,郭显胜,黄永钢,等.80t低频气保恒熔速电渣炉的技术特点及应用[J].中国冶金,2017,27(6):58.(WEI Yajun,GUO Xian-sheng,HUANG Yong-gang,et al.Technical feature and application of 80tESR furnace with low-frequency,gas protection and constant melting rate[J].China Metallurgy,2017,27(6):58.)
[5]茅洪祥,胡汉涛,马国军,等.连铸保护渣对环境的氟污染及其对策[J].炼钢,1999,15(3):41.(MAO Hong-xiang,HU Han-tao,MA Guo-jun,et al.Contamination of fluorine in CC mould powder to environment and countermeasures[J].Steeingmaking,1999,15(3):41.)
[6]赵俊学,尚南,赵忠宇,等.电渣重熔用中氟渣配渣方式对熔点测定的影响[J].钢铁,2018,53(8):44.(ZHAO Jun-xue,SHANG Nan,ZHAO Zhong-yu,et al.Influence of slag preparation mode on melting point of ESR slag with medium fluoride content[J].Iron and Steel,2018,53(8):44.)
[7]李正邦.电渣冶金的理论与实践[M].北京:冶金工业出版社,2010.(LI Zheng-bang.Electroslag Metallurgy Theory and Practice[M].Beijing:Metallurgical Industry Press,2010.)
[8]张晨,刘世洲,王文忠.CaO-SiO2-CaF2三元渣系的挥发率[J].钢铁研究学报,1998,10(6):16.(ZHANG Chen,LIU Shi-zhou,WANG Wen-zhong.Volatility of ternary flux CaOSiO2-CaF2[J].Journal of Iron and Steel Research,1998,10(6):16.)
[9]苗志奇,成国光,李世健,等.工业电渣重熔过程电极插入深度数学模型及应用[J].钢铁,2018,53(9):25.(MIAO Zhiqi,CHENG Guo-guang,LI Shi-jian,et al.Mathematical model of electrode immersing depth in industrial electroslag remelting process and application[J].Iron and Steel,2018,53(9):25.)
[10]陈艳梅,赵俊学,路晓涛,等.CaF2渣系失重与成分变化的试验研究[J].钢铁研究学报,2010,22(12):11.(CHEN Yanmei,ZHAO Jun-xue,LU Xiao-tao,et al.Experimental study on weight loss and compositional variations of slag system bearing bearing CaF2[J].Journal of Iron and Steel Research,2010,22(12):11.)
[11]巨建涛,吕振林,焦志远,等.CaF2-SiO2-CaO渣系的非等温挥发行为[J].过程工程学报,2012,12(4):618.(JU Jiantao,LZhen-Lin,JIAO Zhi-yuan,et al.Non-isothermal analysis on the evaporation behavior of CaF2-SiO2-CaO system slag[J].The Chinese Journal of Process Engineering,2012,12(4):618.)
[12]郭子亮,崔雅茹,赵俊学,等.高铅渣物理化学性能测定的偏差规律[J].辽宁科技大学学报,2016,39(1):47.(GUO Ziliang,CUI Ya-ru,ZHAO Jun-xue,et al.Deviation prediction on physicochemical properties of high-lead slag[J].Journal of university of Science and Technology Liaoning,2016,39(1):47.)
[13]庄迎,李吉东.GA-BP渣系活度预测模型及不锈钢脱氧机理[J].中国冶金,2017,27(1):7.(ZHUANG Ying,LI Jidong.Prediction model of GA-BP molten slag activity and deoxidation mechanism of stainless steel[J].China Metallurgy,2017,27(1):7.)
[14]陈艳梅,赵俊学.电渣冶金过程炉渣成分变化及其影响研究[J].工业加热,2014,43(3):23.(CHEN Yan-mei,ZHAO Jun-xue.Study on slag chemical composition change and its influence during ESR process[J].Industrial Heating,2014,43(3):23.)
[15]郭仲文,王翠香.含CaF2熔渣体系挥发率测定的研究[J],东北工学院学报,1987,52(3):381.(GUO Zhong-wen,WANG Cui-xiang.Study on the volatility measurement for CaF2-cotaining slag systems[J].Journal of Northeastern Polytechnical College,1987,52(3):381.)
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