铝电解槽干式防渗料在电解过程中的反应机理探讨
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摘要
通过对大修铝电解槽中废防渗料的成分和物相组成进行分析,探讨了干式防渗料与电解质的反应机理。研究结果表明,渗透电解质中的NaF和冰晶石均会与干式防渗料反应生成霞石(NaAlSiO_4)玻璃体层,可起到防止电解质进一步向下渗透的作用。但随着渗透电解质的增加,冰晶石会继续与霞石反应生成β氧化铝,β氧化铝层不具有防渗作用,这是导致防渗料中电解质继续渗透的主要原因之一。渗透电解质与防渗料反应还可生成SiF_4气体,使硅元素向防渗料下部迁移,导致废防渗料上层硅元素含量降低。
A component analysis and an X-ray phase analysis of spent dry barrier material were used to reveal the mechanism of deterioration for dry barrier material in aluminum electrolysis cells. The results show that both NaF and cryolite in the osmotic electrolyte react with the dry anti-seepage material to form a glass matrix of nepheline(NaAlSiO_4), which can prevent the electrolyte from further penetrating downward. The Na_3AlF_6 continuously penetrating from the carbon cathode can react with the nephelite to form β-Al_2O_3, and the formation of β-Al_2O_3 is one major cause for deterioration of dry barrier materials. It can also produce SiF_4 gas in the process of electrolyte reacts with dry barrier, which makes the silicon migrate to the lower part and results in the decrease of silicon in the upper layer.
A component analysis and an X-ray phase analysis of spent dry barrier material were used to reveal the mechanism of deterioration for dry barrier material in aluminum electrolysis cells. The results show that both NaF and cryolite in the osmotic electrolyte react with the dry anti-seepage material to form a glass matrix of nepheline(NaAlSiO_4), which can prevent the electrolyte from further penetrating downward. The Na_3AlF_6 continuously penetrating from the carbon cathode can react with the nephelite to form β-Al_2O_3, and the formation of β-Al_2O_3 is one major cause for deterioration of dry barrier materials. It can also produce SiF_4 gas in the process of electrolyte reacts with dry barrier, which makes the silicon migrate to the lower part and results in the decrease of silicon in the upper layer.
引文
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[24]张成行,宋明刚,钱开平,等.铝电解槽用干式保温防渗料的研制及应用[J].耐火材料,2003,(6):339-341.Zhang C X,Song M G,Qian K P,et al.Development and application of insulating dry barrier for aluminum electrolytic cell[J].Refractory Materials.2003,(6):339-341.
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[27]杨帅.基于界面传热机理的铝电解槽综合热场分析模型及其应用[D].长沙:中南大学,2013:67-69.Yang S.An interfacial heat transfer mechanism based integrated model and its application for thermal filed analysis in aluminum reduction[D].Changsha:Central South University,2013:67-69.
[28]Pogodaev A M,Proshkin A V,Polyakov P V,et al.Processes in refractory materials of the cathode assembly of electrolysis cells for aluminum production[J].Russian Journal of Nonferrous Metals,2010,51(4):279-284.
[29]Siljan O J.Sodium aluminium fluoride attack on alumino-silicate refractories-chemical reactions and mineral formation[D].Norway:NTNU.1990:15-20.
[30]李秋霞,刘永成,荆碧,等.SiO2在真空低价氟化法炼铝过程的分布[J].真空科学与技术学报,2011,31(4):490-494.Li Q X,Liu Y C,Jing B,et al.Possible reaction paths of silica in vacuum extraction of aluminum by fluoridization[J].Journal of Vacuum Science and Technology,2011,31(4):490-494.
[31]Lambotte G,Chartrand P.Thermodynamic optimization of the(Na2O+SiO2+NaF+SiF4)reciprocal system using the modified quasichemical model in the quadruplet approximation[J].The Journal of Chemical Thermodynamics,2011,43(11):1678-1699.
[2]包生重,柴登鹏,李晓星,等.含钾盐电解质对干式防渗料渗透的试验研究[J].轻金属,2017,(6):28-32.Bao S C,Chai D P,Li X X,et al.Research on penetration of electrolyte containing potassium salts into dry barrier materials[J].Light Metals.2017,(6):28-32.
[3]Jeltsch R,Chen C.Dry barrier mix in reduction cell cathodes[C]//Carlos E.Suarez.Light Metals.San Diego,USA:John Wiley&Sons Inc,2012:1259-1263.
[4]Morten S,Harald AΦ.Cathodes in Aluminum Electrolysis[M]//Dusseldorf:Aluminum-Verlag Marketing&Kommunikation GmbH,2010:70-72.
[5]刘世英,石忠宁,任必军,等.铝电解槽用干防渗料的导热性与抗渗性[J].中国有色金属学报,2006,16(9):1641-1645.Liu S S,Shi Z N,Ren B J,et al.Thermal conduction and antipenetration of dry barrier powder materials for aluminium electrolytic cells[J].The Chinese Journal of Nonferrous Metals,2006,16(9):1641-1645.
[6]杨贵海,董建雄,孙喜喜,等.干式防渗料在70 kA自焙槽上的应用[J].轻金属,2003,(7):30-33.Yang G H,Dong J X,Sun X X,et al.Applied of dry barrier in 70kA aluminum electrolytic cell[J].Light Metals,2003,(7):30-33.
[7]Pelletier R,Allaire C,Siljan O J,et al.The corrosion of potlining refractories:a unified approach[J].JOM,2001,53(8):18-22.
[8]Sch?ning C,Grande T,Siljan O J.Cathode refractory materials for aluminum reduction cells[C]//C.Edward Eckert.Light Metals.San Diego,USA:John Wiley&Sons Inc,1999:231.
[9]Rutlin J,Grande T.Fluoride attack on alumino-silicate refractories in aluminium electrolysis cells[C]//Huglen R.Light Metals.Warrendale,USA:John Wiley&Sons Inc,1997:295-301.
[10]Brunk F.Corrosion and Behaviour of Fireclay Bricks of Varying Chemical Composition Used in the Bottom Lining of Reduction Cells[C]//Mannweiler U.Light Metals.Warrendale,USA:John Wiley&Sons Inc,1994:834-838.
[11]Dolej?D,Baker D R.Thermodynamic modeling of melts in the system Na2O-NaAlO2-SiO2-F2O[J].Geochimical at Cosmochimica Acta,2005,69(23):5537-5556.
[12]Siljan O J,Junge O,Svendsen T,et al.Experiences with dry barrier powder materials in aluminium electrolysis cells[M]//Light Metals.Warrendale,USA:John Wiley&Sons Inc,1998:573-581.
[13]Lambotte G,Chartrand P.Thermodynamic modeling of the(Al2O3+Na2O),(Al2O3+Na2O+SiO2),and(Al2O3+Na2O+AlF3+NaF)systems[J].The Journal of Chemical Thermodynamics,2013,57(2):306-334.
[14]姚巍,杨贵海,高升志,等.再论干式防渗料在铝电解槽上的应用[C]//中国有色金属学会.提高铝电解槽使用寿命学术研讨会论文集.河南伊川:中国有色金属学会,2004:90-95.Yao W,Yang G H,Gao S Z,et al.Further discussion on dry barrier applied in aluminium electrolytic cell[C]//The Nonferrous Metals Society of China.Proceedings of improving the service life of aluminum reduction cells.Henan Yichuan:The Nonferrous Metals Society of China,2004:90-95.
[15]吕任敏,于海东,张灿辉,等.铝电解槽用干式防渗料[J].耐火材料.2002,36(增刊):73-79.Lyu R M,Yu H D,Zhang C H,et al.Dry barrier for aluminum electrolytic cell[J].Refractory Materials,2002,36(Suppl.):73-79.
[16]吴斌,赵义,王落霞,等.电解槽用抗渗透砖的研制[J].轻金属,2014,(5):28-31.Wu B,Zhao Y,Wang L X,et al.Development of the barrier brick used in aluminum reduction pots[J].Light Metals,2014,(5):28-31.
[17]Neff D V.Clayburn dri-barrier mix its application as a barrier lining in reduction cells[C]//Carlos E.Suarez.Light Metals.San Antonio,USA:John Wiley&Sons,Inc.2013:266-292.
[18]Bittencourt L R,Bonadia P,Valenzuela F A O.Aluminosilicate refractories for aluminum cell linings[J].American Ceramic Society Bulletin.2005,84(2):26-31.
[19]Allaire C.Refractory lining for alumina electrolytic cells[J].Journal of the American Ceramic Society.2010,75(8):2308-2311.
[20]朱新伟,刘双,熊毅.铝电解槽用新型干式防渗料性能的研究[J].轻金属,2009,(10):26-30.Zhu X W,Liu S,Xiong Y.Studies on a new phase plate dry barrier for aluminium electrolytic cell[J].Light Metals,2009,(10):26-30.
[21]张爱芬,马慧侠,白万里.熔融制样-X射线荧光光谱法测定铝电解槽用干式防渗料中主次成分[J].冶金分析,2014,34(5):25-29.Zhang A F,Ma H X,Bai W L.Determination of major and minor components in dry barrier of aluminum electrolytic cell by X-ray fluorescence spectrometry with sample fusion preparation[J].Metallurgical Anaysis.2014,34(5):25-29.
[22]赵更金,吕风雷,苗拥军,等.YS/T 456-2014?铝电解槽用干式防渗料?修订介绍[J].耐火材料,2014,48(6):478-480.Zhao G X,Lyu F L,Miao Y J,et al.Revised introduction of YS/T456-2014 dry barrier powder refractory for aluminum electrolysis cell[J].Refractory.2014,48(6):478-480.
[23]岳建设.铝电解槽用干式防渗耐火材料的开发及防渗机理研究[D].西安,西安理工大学,2007:1-13.Yue J M.Exploit dry damming cell and on theme chanism of study prevent penetrate[D].Xi’an:Xi’an University of Technology,2007:1-13.
[24]张成行,宋明刚,钱开平,等.铝电解槽用干式保温防渗料的研制及应用[J].耐火材料,2003,(6):339-341.Zhang C X,Song M G,Qian K P,et al.Development and application of insulating dry barrier for aluminum electrolytic cell[J].Refractory Materials.2003,(6):339-341.
[25]冯乃祥.铝电解[M].北京:化学工业出版社.2006:203-205.Feng N X.Aluminum Electrolysis[M].Beijing:Chemical Industry Press.2006:203-205.
[26]Bonadia P,Valenzuel F A O,Bittencourt L R,et al.Aluminosilicate refractories for aluminum cell linings[J].American Ceramic Society Bulletin,2005,84(2):26-30.
[27]杨帅.基于界面传热机理的铝电解槽综合热场分析模型及其应用[D].长沙:中南大学,2013:67-69.Yang S.An interfacial heat transfer mechanism based integrated model and its application for thermal filed analysis in aluminum reduction[D].Changsha:Central South University,2013:67-69.
[28]Pogodaev A M,Proshkin A V,Polyakov P V,et al.Processes in refractory materials of the cathode assembly of electrolysis cells for aluminum production[J].Russian Journal of Nonferrous Metals,2010,51(4):279-284.
[29]Siljan O J.Sodium aluminium fluoride attack on alumino-silicate refractories-chemical reactions and mineral formation[D].Norway:NTNU.1990:15-20.
[30]李秋霞,刘永成,荆碧,等.SiO2在真空低价氟化法炼铝过程的分布[J].真空科学与技术学报,2011,31(4):490-494.Li Q X,Liu Y C,Jing B,et al.Possible reaction paths of silica in vacuum extraction of aluminum by fluoridization[J].Journal of Vacuum Science and Technology,2011,31(4):490-494.
[31]Lambotte G,Chartrand P.Thermodynamic optimization of the(Na2O+SiO2+NaF+SiF4)reciprocal system using the modified quasichemical model in the quadruplet approximation[J].The Journal of Chemical Thermodynamics,2011,43(11):1678-1699.