铝用阴极冷捣糊的研究
|
摘要
铝用阴极冷捣糊的施工温度为25～50℃,相比于热捣糊的施工温度100℃左右,冷捣糊的施工温度较低,不需加热,在室温下就能直接使用。冷捣糊具有与热捣糊相媲美的性能,但明显改善了工人施工条件,并减少了对环境的污染。冷捣糊的工业化生产技术一直由美国、法国、日本、挪威等发达国家控制,长期以来对我国施行严密的技术封锁,因此我国急需自主研究和开发冷捣糊并使之产业化。
本文以电煅煤为骨料、中温沥青为粘结剂、蒽油为稀释剂、金属硅粉和硫为粘结剂添加剂,另添加石墨和TiB2制备铝用阴极冷捣糊。研究了颗粒组成,蒽油加入量对粘结剂炭化率的影响；粘结剂不同配比对试样灰分、挥发份、体积密度、抗压强度、电阻率、真密度、收缩率、抗钠侵蚀的影响；试样在焙烧过程中物相变化；添加剂对试样的性能影响；以及石墨和TiB2加入量对试样的影响。研究结果表明：
(1)颗粒级配对冷捣糊的物理性能有较大的影响,对焙烧后的试样性能研究表明,当粒度分布系数n为0.45时,性能较好。
(2)当粘结剂中蒽油加入量为30%时,冷捣糊体积密度较大,电阻率最小,灰分、挥发份、真密度、收缩率都比较优秀。随着葸油加入量增加,煤沥青的析焦率降低。
(3)由于金属硅粉、硫能提高煤沥青的析焦率,因此随着加入量的增加,捣打料的体积密度、抗压强度都有不同程度的提高；研究表明,当金属硅粉、铝粉加入量分别为3%、2.5%时,试样的强度、体积密度、电阻率、收缩率较好。
(4)石墨的加入有利于试样电阻率降低,但不利于试样的抗压强度。添加剂TiB2具有良好的抗钠渗透性能,它的加入能减小炭块阴极的钠膨胀。
(5)通过对试样进行差重分析,分析了试样在焙烧过程中物相变化,研究了粘结剂作用机理,有利于对产品性能分析。
The placement temperature of cold ramming paste for aluminium electrolysis is 25～50℃against 100℃of hot ramming paste for aluminium electrolysis. The cold ramming paste for aluminium electrolysis can be used at room temperature without heating. The characteristics of the cold ramming paste are as good as hot ramming paste for aluminium electrolysis after roasting. However the placement environment can be improved obviously and the environmental pollution can be reduced greatly. The technology of cold ramming paste for aluminium electrolysis is controlled by some developed counties for example America, Canada, Japan, Norway and so on. The independent technology of cold ramming paste for aluminium electrolysis needs to be developed and applied to production presently because of the technological blockade against our country.
The cold ramming paste for aluminium electrolysis has been studied in the paper with electrically calcined anthracite as aggregate, soft pitch as binder, anthroic oil as thinner, metallic Si powder and sulfur powder as additive for binder and adding some graphite and TiB2-The effect of the grain size distribution and the added quantity of anthroic oil on carbonization rata of binder has been studied. The effect of the ratio of blinder on the ash content, volatile components, density of rock, compressive strength, resistively, skeletal density, shrinkage rate and erosion resistance of Na has also been studied. Then the phase analysis has been researched. Finally, the effect of additive added quantity of graphite and TiB2 on the samples has been studied. The results show that:
(1) The particle size distribution has a great influence on physical properties. The research on the sample baked show that the physical of sample is best when the particle size distribution parameter (n) is 0.45.
(2) The coke yield decreases with increasing the content of anthroic oil. The density of rock is big, the resistively is small and the ash content, volatile components, skeletal density and shrinkage rate is good when the content of anthroic oil is 30%.
(3) The density of rock and compressive strength increase because the coke yield of cold ramming paste increases by adding metallic Si powder and sulfur powder. The results show that the compressive strength, density of rock, resistance rate and shrinkage rate of sample is good when the added quantities of metallic Si and sulfur powder are 3% and 2.5% respectively.
(4) The resistance rate decreases by adding graphite which also has a negative effect on the compressive strength of sample. The erosion resistance of Na increases by adding TiB2 because the bulge of Na in carbon block cathode decreases.
(5)The phase analysis has been researched in the baking process by TGA (thermogravimetric analysis). And the mechanism of thinner has also been studied. Then the researches have a positive effect on the characters of the products.
本文以电煅煤为骨料、中温沥青为粘结剂、蒽油为稀释剂、金属硅粉和硫为粘结剂添加剂,另添加石墨和TiB2制备铝用阴极冷捣糊。研究了颗粒组成,蒽油加入量对粘结剂炭化率的影响；粘结剂不同配比对试样灰分、挥发份、体积密度、抗压强度、电阻率、真密度、收缩率、抗钠侵蚀的影响；试样在焙烧过程中物相变化；添加剂对试样的性能影响；以及石墨和TiB2加入量对试样的影响。研究结果表明：
(1)颗粒级配对冷捣糊的物理性能有较大的影响,对焙烧后的试样性能研究表明,当粒度分布系数n为0.45时,性能较好。
(2)当粘结剂中蒽油加入量为30%时,冷捣糊体积密度较大,电阻率最小,灰分、挥发份、真密度、收缩率都比较优秀。随着葸油加入量增加,煤沥青的析焦率降低。
(3)由于金属硅粉、硫能提高煤沥青的析焦率,因此随着加入量的增加,捣打料的体积密度、抗压强度都有不同程度的提高；研究表明,当金属硅粉、铝粉加入量分别为3%、2.5%时,试样的强度、体积密度、电阻率、收缩率较好。
(4)石墨的加入有利于试样电阻率降低,但不利于试样的抗压强度。添加剂TiB2具有良好的抗钠渗透性能,它的加入能减小炭块阴极的钠膨胀。
(5)通过对试样进行差重分析,分析了试样在焙烧过程中物相变化,研究了粘结剂作用机理,有利于对产品性能分析。
The placement temperature of cold ramming paste for aluminium electrolysis is 25～50℃against 100℃of hot ramming paste for aluminium electrolysis. The cold ramming paste for aluminium electrolysis can be used at room temperature without heating. The characteristics of the cold ramming paste are as good as hot ramming paste for aluminium electrolysis after roasting. However the placement environment can be improved obviously and the environmental pollution can be reduced greatly. The technology of cold ramming paste for aluminium electrolysis is controlled by some developed counties for example America, Canada, Japan, Norway and so on. The independent technology of cold ramming paste for aluminium electrolysis needs to be developed and applied to production presently because of the technological blockade against our country.
The cold ramming paste for aluminium electrolysis has been studied in the paper with electrically calcined anthracite as aggregate, soft pitch as binder, anthroic oil as thinner, metallic Si powder and sulfur powder as additive for binder and adding some graphite and TiB2-The effect of the grain size distribution and the added quantity of anthroic oil on carbonization rata of binder has been studied. The effect of the ratio of blinder on the ash content, volatile components, density of rock, compressive strength, resistively, skeletal density, shrinkage rate and erosion resistance of Na has also been studied. Then the phase analysis has been researched. Finally, the effect of additive added quantity of graphite and TiB2 on the samples has been studied. The results show that:
(1) The particle size distribution has a great influence on physical properties. The research on the sample baked show that the physical of sample is best when the particle size distribution parameter (n) is 0.45.
(2) The coke yield decreases with increasing the content of anthroic oil. The density of rock is big, the resistively is small and the ash content, volatile components, skeletal density and shrinkage rate is good when the content of anthroic oil is 30%.
(3) The density of rock and compressive strength increase because the coke yield of cold ramming paste increases by adding metallic Si powder and sulfur powder. The results show that the compressive strength, density of rock, resistance rate and shrinkage rate of sample is good when the added quantities of metallic Si and sulfur powder are 3% and 2.5% respectively.
(4) The resistance rate decreases by adding graphite which also has a negative effect on the compressive strength of sample. The erosion resistance of Na increases by adding TiB2 because the bulge of Na in carbon block cathode decreases.
(5)The phase analysis has been researched in the baking process by TGA (thermogravimetric analysis). And the mechanism of thinner has also been studied. Then the researches have a positive effect on the characters of the products.
引文
[1]姚海林,张桐林,张泉林.冷捣糊在自焙槽阴极捣固中的应用[J].轻金属,1997(11)：31-35.
[2]李庚宏等.铝用炭素材料[J].炭紊技术.2001,NO.2,45-47.
[3]吴智明,张平,王平等.铝电解用高石墨质阴极炭块的应用分析及工业实践[J].世界有色金属,2006,6：19-25.
[4]许斌,潘立慧.炭材料用煤沥青的制备、性能和应用[M].武汉：湖北科学技术出版社2002.76-78.
[5]Carolaa cuna,Petroleum pitch,a real altenrative to coal tar pitch as binder material for anode production[J],Light metals,1997,549-554.
[6]Hitomi Hatano, et al,lmprovement and control of the quality of binder pitch for graphite electrodes[J],Fuel,1989,68,1503-1506.
[7]R.T.Lewis et al,Baden-BadenA bstract[J],2B.1986,78-80.
[8]邱竹贤,有色冶金冶金学[M],冶金工业出版社,45-46.
[9]D.M.Riggs,Polyer For Fibers and Elastomers[J], ACS Symposium Series,No,260,Jittc.Arthur, Jr.l Edition,1984,245-248.
[10]续正国.鞍钢化工总厂改质沥青引进技术的调查[J].轻金属,1983(1)：39-40.
[11]朱旺喜,邱竹贤.用蒽油作稀释剂的冷捣糊性能[J].轻金属,1992(7)：45-47.
[12]樊留锁.冷捣糊的实验和讨论[J].炭素技术,1994(1)：12-14.
[13]胨蔚然,电碳技术[J].1981,No 3,12-14.
[14][苏]弗.耶普里瓦洛夫米阿,斯捷潘年科,煤沥青.吉林炭素厂译.
[15][俄]HA. C a E B 14 H a等,炭紊技术,1992,No.6.21-23(中译文).
[16][苏]M. B. roⅡT M a H等,国外炭紊,1980.No4.1-6.
[17][苏]弗.耶普里瓦洛夫米阿,斯捷潘年科,煤沥青.吉林炭紊厂译.
[18]许斌,潘立慧.炭材料用煤沥青的制备、性能和应用[M].武汉：湖北科学技术出版社,2002.113-110.
[19]Mochida l,et al, Carbonization of pitch:compatibility of components in carbonization[J] Fuel.1977,56(1):49-56.
[20]Kershaw J R,Smart P J, Extraction of coal-tar pitch and the efect on carbonization[J],Carbon, 1994.32 (1):85-92.
[21]Qian S-A, et al, Structural characterization of pitch fee dstocks for coke making[J], Fuel.1985,64(8):1085-1087.
[22]童芳森,许斌李哲浩.炭素材料生产问答[M].北京：冶金工业出版社1991.124.
[23]Jaques Lahaye,沥青与焦碳的相互作用[J],炭素技术,1987,2：7-12.
[24]Lewisl C,The chemistry of pitch carbonization[J],Fuel,1987,66(11):1527-1533.
[25]李圣华,石墨电极生产[M],北京,冶金工业出版社,1997,244-248.
[26]Daniel Dumas, Regis Paulus, Simon Meseguer. A NEW RAMMING PASTE FOR THE ALUMINUM ELECTROLYSIS CELL COMPATIBLE WITH TECHNICAL AND ENVOROMMENTAL CONSTRAINTS, TMS,2002, Seattle Washington.
[27]许文彪,王平甫,李庆宏.铝用阴极冷捣糊料的实验与研究[J].炭素技术,1992(4)：22-26.
[28]李庚宏,现代铝电解新技术汇编.内部资料,133-41.
[29]王凤旗,郭志刚,郝凤双,周自明.低温用冷捣糊的研制[J].炭素科技,2000,10(2)：31-33.
[30]路忠胜.低捣固温度铝用冷捣糊的研究[J].轻金属,2000(9)：50-51.
[31]周国斌.粘结剂含量对铝电解槽阴极捣固糊质量的影响研究[J].碳素技术,2007(2)：34-38.
[32]林南如主编.无机非金属材料测试方法(第一版)[M].武汉：武汉工业大学出版社,1990.
[33]C C Furnas. Grading aggregates-Ⅰ-mathematical relations for beds of broken solids of maximum density [J]. Ind Eng Chemistry,1931,23(9):1052-1058.
[34]C C Furnas. Relations volume between specific voids, and size composition in systems of broken solids of mixed sizes [R]. U S Bureau of Mines Reports of Investigations,1928,12: 28-94.
[35]A H M Andreasen. Uber die Guhigkeit des stokes schen gesetzes fur nicht kugelformige teilchen[J]. Kolloid Z,1929,49(2):175-179.
[36]A H M Andersen. Uber die Beziehung zwischen und Zwischenraum in Produekten aus losen Kornern (mit einigen experimenten) [J]. Kolloid—Z,1930,50(3):217-228.
[37]J E Funk, D R Dinger. Particle packing, part Ⅰ: funamentals of particle packing monodisperse spheres [J]. Interceram,1992,41(1):10-14.
[38]D R Dinger, J E Funk. Particle packing, part Ⅱ: review of of packing poly disperse particle system [J]. Interceram,1992,41(2):95-97.
[39]D R Dinger,J E Funk. Particle packing, part Ⅲ: Discrete versus continuous particle sizes[J]. Interceram,1992,41(5):332-334.
[40]D R Dinger, J E Funk. Particle packing, part Ⅳ: computer ofmodelling particle packing phenomena [J]. Interceram,1993,42(3):150-153.
[41]D R Dinger, J E Funk. Particle packing, part Ⅴ: computational methods applied to experimental distributions [J]. Interceram,1994,43(2):87-89.
[42]高云琴,薛群虎,段锋,张颖.粒度分布对干式冷捣糊性能的影响[J].西安建筑科技大学学报(自然科学版),2008,40(6)：764-768.
[43]张永娟,张雄.粉煤灰水泥堆积效应与其抗压强度的关系[J].2007,10(1)：43-47.
[44]祝洪喜,邓承继,白晨,罗星源.耐火材料连续颗粒分布的紧密堆积模型[J].武汉科技大学学报(自然科学版),2008,31(2)：159-165.
[45]黄永忠等.铝电解生产[M]长沙：中南工业大学出版社.1994.
[46]路忠胜.中国铝用阴极糊生产技术的进步[J].炭素科技,2002,12(3)：19-21.
[47]M sorlie, H A Oye.Cathode in Aluminium Electrolysis[M].2edition. copyright by Aluminium—VerIag Gmbh, Dusseldorf,1994.
[48]冯乃祥.冰晶石熔体和金属Na在铝电解阴极碳块中的共同渗透[J].金属学报,1999.35(6)：6-11.
[49]刘世英等.石墨含量对阴极炭块渗透性的影响[J],炭素技术,2008,(5)：1-4.
[50]徐军莉等.氟化钾体系中电沉积制取铝电解用TiB2惰性阴极[J].中国国际铝冶金技术论坛论文集.2007.289-293.
[51]陶著,许斌.应用差热和热失重分析对煤沥青热解过程的研究[J].碳素,1987,(1)：20-22.
[52]孙戈.炭—沥青组分在焙烧过程中物理量连续变化的研究[J].碳素,1990,(1)：12-16
[53]许斌,丁洪武.焙烧过程中煤沥青枯结剂行为分析[J]碳素,1993, (4)：16-17.
[54]朱静,金鸣林.欧阳林等.沥青质差热分析[J]燃料与化学,2000, (4)：204-206.
[55]龚景松,傅维镶.沥青燃料的热解特性研究[J].冶金能源,2002,21(4)：36-38.
[56][苏]弗.耶普里瓦洛夫,米.阿.斯捷潘年科煤沥青[M],吉林炭素厂译.
[57]郭德英等.升温速率对煤沥青热解缩聚的影响[J],炭素技术,2004,23.
[2]李庚宏等.铝用炭素材料[J].炭紊技术.2001,NO.2,45-47.
[3]吴智明,张平,王平等.铝电解用高石墨质阴极炭块的应用分析及工业实践[J].世界有色金属,2006,6：19-25.
[4]许斌,潘立慧.炭材料用煤沥青的制备、性能和应用[M].武汉：湖北科学技术出版社2002.76-78.
[5]Carolaa cuna,Petroleum pitch,a real altenrative to coal tar pitch as binder material for anode production[J],Light metals,1997,549-554.
[6]Hitomi Hatano, et al,lmprovement and control of the quality of binder pitch for graphite electrodes[J],Fuel,1989,68,1503-1506.
[7]R.T.Lewis et al,Baden-BadenA bstract[J],2B.1986,78-80.
[8]邱竹贤,有色冶金冶金学[M],冶金工业出版社,45-46.
[9]D.M.Riggs,Polyer For Fibers and Elastomers[J], ACS Symposium Series,No,260,Jittc.Arthur, Jr.l Edition,1984,245-248.
[10]续正国.鞍钢化工总厂改质沥青引进技术的调查[J].轻金属,1983(1)：39-40.
[11]朱旺喜,邱竹贤.用蒽油作稀释剂的冷捣糊性能[J].轻金属,1992(7)：45-47.
[12]樊留锁.冷捣糊的实验和讨论[J].炭素技术,1994(1)：12-14.
[13]胨蔚然,电碳技术[J].1981,No 3,12-14.
[14][苏]弗.耶普里瓦洛夫米阿,斯捷潘年科,煤沥青.吉林炭素厂译.
[15][俄]HA. C a E B 14 H a等,炭紊技术,1992,No.6.21-23(中译文).
[16][苏]M. B. roⅡT M a H等,国外炭紊,1980.No4.1-6.
[17][苏]弗.耶普里瓦洛夫米阿,斯捷潘年科,煤沥青.吉林炭紊厂译.
[18]许斌,潘立慧.炭材料用煤沥青的制备、性能和应用[M].武汉：湖北科学技术出版社,2002.113-110.
[19]Mochida l,et al, Carbonization of pitch:compatibility of components in carbonization[J] Fuel.1977,56(1):49-56.
[20]Kershaw J R,Smart P J, Extraction of coal-tar pitch and the efect on carbonization[J],Carbon, 1994.32 (1):85-92.
[21]Qian S-A, et al, Structural characterization of pitch fee dstocks for coke making[J], Fuel.1985,64(8):1085-1087.
[22]童芳森,许斌李哲浩.炭素材料生产问答[M].北京：冶金工业出版社1991.124.
[23]Jaques Lahaye,沥青与焦碳的相互作用[J],炭素技术,1987,2：7-12.
[24]Lewisl C,The chemistry of pitch carbonization[J],Fuel,1987,66(11):1527-1533.
[25]李圣华,石墨电极生产[M],北京,冶金工业出版社,1997,244-248.
[26]Daniel Dumas, Regis Paulus, Simon Meseguer. A NEW RAMMING PASTE FOR THE ALUMINUM ELECTROLYSIS CELL COMPATIBLE WITH TECHNICAL AND ENVOROMMENTAL CONSTRAINTS, TMS,2002, Seattle Washington.
[27]许文彪,王平甫,李庆宏.铝用阴极冷捣糊料的实验与研究[J].炭素技术,1992(4)：22-26.
[28]李庚宏,现代铝电解新技术汇编.内部资料,133-41.
[29]王凤旗,郭志刚,郝凤双,周自明.低温用冷捣糊的研制[J].炭素科技,2000,10(2)：31-33.
[30]路忠胜.低捣固温度铝用冷捣糊的研究[J].轻金属,2000(9)：50-51.
[31]周国斌.粘结剂含量对铝电解槽阴极捣固糊质量的影响研究[J].碳素技术,2007(2)：34-38.
[32]林南如主编.无机非金属材料测试方法(第一版)[M].武汉：武汉工业大学出版社,1990.
[33]C C Furnas. Grading aggregates-Ⅰ-mathematical relations for beds of broken solids of maximum density [J]. Ind Eng Chemistry,1931,23(9):1052-1058.
[34]C C Furnas. Relations volume between specific voids, and size composition in systems of broken solids of mixed sizes [R]. U S Bureau of Mines Reports of Investigations,1928,12: 28-94.
[35]A H M Andreasen. Uber die Guhigkeit des stokes schen gesetzes fur nicht kugelformige teilchen[J]. Kolloid Z,1929,49(2):175-179.
[36]A H M Andersen. Uber die Beziehung zwischen und Zwischenraum in Produekten aus losen Kornern (mit einigen experimenten) [J]. Kolloid—Z,1930,50(3):217-228.
[37]J E Funk, D R Dinger. Particle packing, part Ⅰ: funamentals of particle packing monodisperse spheres [J]. Interceram,1992,41(1):10-14.
[38]D R Dinger, J E Funk. Particle packing, part Ⅱ: review of of packing poly disperse particle system [J]. Interceram,1992,41(2):95-97.
[39]D R Dinger,J E Funk. Particle packing, part Ⅲ: Discrete versus continuous particle sizes[J]. Interceram,1992,41(5):332-334.
[40]D R Dinger, J E Funk. Particle packing, part Ⅳ: computer ofmodelling particle packing phenomena [J]. Interceram,1993,42(3):150-153.
[41]D R Dinger, J E Funk. Particle packing, part Ⅴ: computational methods applied to experimental distributions [J]. Interceram,1994,43(2):87-89.
[42]高云琴,薛群虎,段锋,张颖.粒度分布对干式冷捣糊性能的影响[J].西安建筑科技大学学报(自然科学版),2008,40(6)：764-768.
[43]张永娟,张雄.粉煤灰水泥堆积效应与其抗压强度的关系[J].2007,10(1)：43-47.
[44]祝洪喜,邓承继,白晨,罗星源.耐火材料连续颗粒分布的紧密堆积模型[J].武汉科技大学学报(自然科学版),2008,31(2)：159-165.
[45]黄永忠等.铝电解生产[M]长沙：中南工业大学出版社.1994.
[46]路忠胜.中国铝用阴极糊生产技术的进步[J].炭素科技,2002,12(3)：19-21.
[47]M sorlie, H A Oye.Cathode in Aluminium Electrolysis[M].2edition. copyright by Aluminium—VerIag Gmbh, Dusseldorf,1994.
[48]冯乃祥.冰晶石熔体和金属Na在铝电解阴极碳块中的共同渗透[J].金属学报,1999.35(6)：6-11.
[49]刘世英等.石墨含量对阴极炭块渗透性的影响[J],炭素技术,2008,(5)：1-4.
[50]徐军莉等.氟化钾体系中电沉积制取铝电解用TiB2惰性阴极[J].中国国际铝冶金技术论坛论文集.2007.289-293.
[51]陶著,许斌.应用差热和热失重分析对煤沥青热解过程的研究[J].碳素,1987,(1)：20-22.
[52]孙戈.炭—沥青组分在焙烧过程中物理量连续变化的研究[J].碳素,1990,(1)：12-16
[53]许斌,丁洪武.焙烧过程中煤沥青枯结剂行为分析[J]碳素,1993, (4)：16-17.
[54]朱静,金鸣林.欧阳林等.沥青质差热分析[J]燃料与化学,2000, (4)：204-206.
[55]龚景松,傅维镶.沥青燃料的热解特性研究[J].冶金能源,2002,21(4)：36-38.
[56][苏]弗.耶普里瓦洛夫,米.阿.斯捷潘年科煤沥青[M],吉林炭素厂译.
[57]郭德英等.升温速率对煤沥青热解缩聚的影响[J],炭素技术,2004,23.