高磷硅锰合金还原脱磷实验研究
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摘要
在硅钼炉中,1400℃的条件下,利用硅钙合金、稀土硅、铝基脱磷剂等对高磷硅锰合金进行还原脱磷实验研究.脱磷实验采用CaO-CaF2(质量比为25∶75)为覆盖渣,渣金比为0.2∶1.采用ICP光谱仪检测脱磷后合金中的磷含量,X射线衍射检测渣样物相成分,着重分析了不同脱磷剂及其用量对高磷硅锰合金还原脱磷的影响.结果表明:随脱磷剂用量的增加,硅锰合金脱磷率呈上升的趋势.其中,铝基脱磷剂脱磷效果最好,当其质量分数达到8%时,合金中磷的质量分数可降至0.21%,符合国标要求(≤0.25%),脱磷率达78%;硅钙合金次之,当其质量分数达到10%时,脱磷率为47%;稀土硅的脱磷效果最差,当其质量分数达10%时,脱磷率仅22%.铝基脱磷剂为本实验条件下的最佳脱磷剂.
There are abundant manganese mineral resources in Chengkou and Xiushang County,Chongqing City,as well as a phosphorus content that is over the national standard;thus,the mass percent of phosphorous in Si-Mn alloys produced from manganese ores is over 1%.This can easily result in "cold brittleness"and reduce the steel quality when the alloys are used for deoxidation and alloying in steelmaking.Therefore,it is important to research on the dephosphorization of Si-Mn alloy.Dephosphorization of a highphosphorus Si-Mn alloy was studied under dephosphorizing agents of Si-Ca alloy,rare earth silicon,and Al-based dephosphorizer in a silicon molybdenum furnace of 1400 ℃.In the experiment,CaO-CaF2(mass ratio of 25∶75) was used as a covering slag,and the ratio of slag-metal is 0.2∶1.The phosphorous content in the Si-Mn alloy after dephosphorizatoin was detected by an inductively coupled plasma(ICP) spectrometer,and the phase composition of the slag was analyzed by X-ray diffractometry(XRD).The effects of different dephosphorizing agents and their dephosphorization rates were analyzed.The results show that the dephosphorization rate increases with dephosphorizer content.For Al-based dephosphorizer,the dephosphorization effect is optimum at 8% dephosphorizer content,whereby the phosphorus content in the Si-Mn alloy is reduced to 0.21%,which meets the national standard(≤0.25%),and the dephosphorization rate reaches 78%.The efficiency of Si-Ca alloy is lower;the dephosphorization rate is 47% even when the alloy content reaches 10%.The effect of rare earth silicon is the least;the dephosphorization rate is 22% when the content reaches 10%.Thus,the Al-based dephosphorizer is the best dephosphorization agent under the present experimental conditions.
There are abundant manganese mineral resources in Chengkou and Xiushang County,Chongqing City,as well as a phosphorus content that is over the national standard;thus,the mass percent of phosphorous in Si-Mn alloys produced from manganese ores is over 1%.This can easily result in "cold brittleness"and reduce the steel quality when the alloys are used for deoxidation and alloying in steelmaking.Therefore,it is important to research on the dephosphorization of Si-Mn alloy.Dephosphorization of a highphosphorus Si-Mn alloy was studied under dephosphorizing agents of Si-Ca alloy,rare earth silicon,and Al-based dephosphorizer in a silicon molybdenum furnace of 1400 ℃.In the experiment,CaO-CaF2(mass ratio of 25∶75) was used as a covering slag,and the ratio of slag-metal is 0.2∶1.The phosphorous content in the Si-Mn alloy after dephosphorizatoin was detected by an inductively coupled plasma(ICP) spectrometer,and the phase composition of the slag was analyzed by X-ray diffractometry(XRD).The effects of different dephosphorizing agents and their dephosphorization rates were analyzed.The results show that the dephosphorization rate increases with dephosphorizer content.For Al-based dephosphorizer,the dephosphorization effect is optimum at 8% dephosphorizer content,whereby the phosphorus content in the Si-Mn alloy is reduced to 0.21%,which meets the national standard(≤0.25%),and the dephosphorization rate reaches 78%.The efficiency of Si-Ca alloy is lower;the dephosphorization rate is 47% even when the alloy content reaches 10%.The effect of rare earth silicon is the least;the dephosphorization rate is 22% when the content reaches 10%.Thus,the Al-based dephosphorizer is the best dephosphorization agent under the present experimental conditions.
引文
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[14]Ban B Y,Bai X L,Li J W,et al.The mechanism of P removal by solvent refining in Al--Si--P system.Metall Mater Trans B,2015,46(6):2430
[15]Li H Y,Sun Y,Bin J,et al.Effect of cerium on as-cast microstructure and properties of heat-resistant aluminum conductor.J Central S Univ Sci Technol,2011,42(10):3026(李红英,孙远,宾杰,等.Ce对耐热铝导体材料铸态组织和性能的影响.中南大学学报(自然科学版),2011,42(10):3026)
[16]Wu C J,Cheng S W,Huang D Q.Grain-boundary segregation of rare earths and phosphorus in hardened steel during tempering.J Beijing Univ Iron Steel Technol,1980(1):85(吴承建,程述武,黄德清.稀土、磷等元素在淬火钢回火时的晶界偏聚.北京钢铁学院学报,1980(1):85)
[17]Liu X,Yang J C,Gao X Z.Effects of RE on the inclusions and impact toughness of 2Cr13 stainless steel.J Univ Sci Technol Beijing,2010,32(5):605(刘晓,杨吉春,高学中.稀土对2Cr13不锈钢夹杂物的变质及对冲击韧性的影响.北京科技大学学报,2010,32(5):605)
[18]Shi L M,Zhu D Y,Luo X B.Investigation of the effect of rareearth element Ce on graphite spheroidization.Foundry Technol,2008,29(10):1364(石丽敏,朱定一,罗晓斌.稀土元素Ce对石墨球化作用的研究.铸造技术,2008,29(10):1364)
[19]Lu L,Zhu D Y,Wang C L.Effects of Mn and Ce additions on structures and properties of Fe-Ni-Mn-C-Si-Ce alloys.Chin J Nonferrous Met,2007,17(6):909(卢铃,朱定一,汪才良.Mn和Ce对Fe--Ni-Mn-C-Si--Ce系合金组织和性能的影响.中国有色金属学报,2007,17(6):909)
[2]Kanungo S B,Mishra S K.Dephosphorization of high-phosphorus manganese ores of southern Orissa and Andhra Pradesh,India,by roasting with sodium chloride followed by leaching in dilute nitric acid.Miner Process Extr Metall,2013,109(3):C145
[3]Guo H H,Song B,Mao J H,et al.Study on phosphorus segregation of weathering resistance steel//Proceedings of National Physical and Chemical of Metallurgy Meeting.Jinan,2006:431(郭宏海,宋波,毛璟红,等.耐候钢中磷元素偏析行为研究//全国冶金物理化学学术会议论文集.济南,2006:431)
[4]Zhu L J,Wu D,Zhao X M.Effect of silicon content on thermodynamics of austenite decomposition in C-Si-Mn TRIP steels.J Iron Steel Res Int,2006,13(3):57
[5]Tabuchi S,Sano N.Thermodynamics of phosphate and phosphide in Ca O--Ca F2melts.Metall Trans B,1984,15(2):351
[6]Shin J H,Park J H.Thermodynamics of reducing refining of phosphorus from Si--Mn alloy using Ca O--Ca F2slag.Metall Mater Trans B,2012,43(6):1243
[7]Masumitsu N,Ito K,Fruehan R J.Thermodynamics of Ca-Ca F2and Ca-Ca Cl2systems for the dephosphorization of steel.Metall Trans B,1988,19(4):643
[8]Ni R M,Cheng W,Wei S K.Study on dephosphorization of silico-manganese ferroalloy under reducing atmosphere with metallic calcium.Iron Steel,1989(9):49(倪瑞明,成武,魏寿昆.金属钙对硅锰合金脱磷的研究.钢铁,1989(9):49)
[9]Zeng S L,Liu J,Li H.Experiments on outside furnace dephosphorization for ferromanganese-silicon.Ferro-alloys,2004(1):1(曾世林,刘军,李辉.锰硅合金炉外脱磷试验研究.铁合金,2004(1):1)
[10]Wen X S,Li H Y,Sun Y D.Application of reduction dephosphorization on low or extra low carbon ferro-manganese-silicon.Ferro-alloys,2011(2):1(闻昕舒,李海云,孙岩铎.低碳锰硅、微碳锰硅铁合金还原脱磷的应用.铁合金,2011(2):1)
[11]Meteleva-Fischer Y,Yang Y,Boom R,et al.Alloying refining of metallurgical grade sillicon with rare earth elements//TMS2013.Texas,2013:201
[12]Tang K,Lvvik O M,Safarian J,et al.Removal of phosphorus in metallurgical silicon by rare earth elements.Metall Mater Trans E,2014,1(3):257
[13]Liang L K,Zhou H M,Yang H,et al.Possibility of using CaAl alloy in reductive dephosphorization.Iron Steel,1991,26(6):16(梁连科,周昊明,杨怀,等.Ca--Al合金在还原脱磷中应用的可能性.钢铁,1991,26(6):16)
[14]Ban B Y,Bai X L,Li J W,et al.The mechanism of P removal by solvent refining in Al--Si--P system.Metall Mater Trans B,2015,46(6):2430
[15]Li H Y,Sun Y,Bin J,et al.Effect of cerium on as-cast microstructure and properties of heat-resistant aluminum conductor.J Central S Univ Sci Technol,2011,42(10):3026(李红英,孙远,宾杰,等.Ce对耐热铝导体材料铸态组织和性能的影响.中南大学学报(自然科学版),2011,42(10):3026)
[16]Wu C J,Cheng S W,Huang D Q.Grain-boundary segregation of rare earths and phosphorus in hardened steel during tempering.J Beijing Univ Iron Steel Technol,1980(1):85(吴承建,程述武,黄德清.稀土、磷等元素在淬火钢回火时的晶界偏聚.北京钢铁学院学报,1980(1):85)
[17]Liu X,Yang J C,Gao X Z.Effects of RE on the inclusions and impact toughness of 2Cr13 stainless steel.J Univ Sci Technol Beijing,2010,32(5):605(刘晓,杨吉春,高学中.稀土对2Cr13不锈钢夹杂物的变质及对冲击韧性的影响.北京科技大学学报,2010,32(5):605)
[18]Shi L M,Zhu D Y,Luo X B.Investigation of the effect of rareearth element Ce on graphite spheroidization.Foundry Technol,2008,29(10):1364(石丽敏,朱定一,罗晓斌.稀土元素Ce对石墨球化作用的研究.铸造技术,2008,29(10):1364)
[19]Lu L,Zhu D Y,Wang C L.Effects of Mn and Ce additions on structures and properties of Fe-Ni-Mn-C-Si-Ce alloys.Chin J Nonferrous Met,2007,17(6):909(卢铃,朱定一,汪才良.Mn和Ce对Fe--Ni-Mn-C-Si--Ce系合金组织和性能的影响.中国有色金属学报,2007,17(6):909)