铝用炭阳极制备关键技术研究及工程化应用
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摘要
炭阳极质量在铝电解生产中起着举足轻重的作用,深入研究炭阳极生产工艺规律和相关理论、开发优质炭阳极生产技术是我国现代铝工业亟待解决的重大课题。本文针对我国我国铝用炭阳极用石油焦和煤沥青地域和生产特征开展了系统的基础理论研究,并结合我国炭阳极生产实践开展了系列工艺优化和工程化技术创新研究,获得了如下理论和应用研究成果。
(1)首次系统研究了我国石油焦性质的地域分布特征,结果表明,东北部所产石油焦,硫、钒含量较低,是生产炭阳极产品的优质原料,但量少价高,对生产铝用炭阳极不具经济性；华北、华中地区的炼油厂部分掺配了进口原油,所产石油焦钒、硫含量比使用国产原油生产的石油焦要高得多,且钙含量也普遍较高；华南地区的炼油厂主要使用进口原油生产石油焦,所产石油焦中的硫、钒含量很高,但钙、铁含量较低。
(2)系统研究了我国石油焦特性与炭阳极质量的关联度,揭示了石油焦中微量元素之间的耦合作用行为及其对炭的氧化催化和反催化的影响规律；在此基础上创造性地开发了石油焦选择性耦合混配均质化技术,拓宽了铝用炭阳极的可利用资源。
(3)首次系统研究了我国采用热聚法生产煤沥青的特性,揭示了中间相以及QI等固体相对煤沥青性质的影响规律,结果表明,高温热聚法生产的煤沥青中甲苯不溶物、喹啉不溶物以及中间相含量较高,相同温度下的粘度比闪蒸法生产的煤沥青高3-5倍,对混捏效果和生阳极质量均造成负面影响。
(4)首次将石油焦选择性耦合混配均质化技术、干料配方新技术、球磨粉在线监测及控制技术、残极清理及大颗粒洁净残极配方技术、热聚法煤沥青的混捏新技术、高温均质化焙烧技术等创新集成,形成了优质阳极制备成套关键技术,并成功实现了工程化应用,取得了显著的经济、社会和环境效益。
Anode quality plays an important role for the performance of aluminum smelting cells. Therefore, the thorough study on the production process characteristics and fundamental theories and key-technology development for producing high quality prebaked anodes become an important and urgent research project for Chinese aluminum industry. Focusing on the regionalism and production characteristics of aluminiun-consuming anode coke and coal tar pitch, this paper carried out a fundamental research systematically. And combining with Chinese carbon anode production practice, series of process optimization and engineering technological innovation research were carried out. The theoretical and applied research results were obtained as follow:
(1) A study on the regional distribution characteristics of the properties of Chinese domestic petroleum coke was first systematically carried out. The study results showed that the petroleum coke produced by northeast, with a lower content of S and V element, is the high-quality raw material for carbon anode production. However, it is of low amount and high price, and non-economic for anode production. Refinery in north and central China, which used import crude oil partly, produced petroleum coke with a higher content of V, S and Ca than those produced with domestic crude oil. Refinery in south China mainly used import crude oil and produced petroleum coke with high S, V content, and low Ca, Fe content.
(2) The relation between the characteristics of cokes and carbon anode qualities in our country were studied comprehensively. The study results revealed the coupling effects behavior of the microelements in cokes and their influences of the catalysis and inhibition on carbon oxidation. Based on the study results, a selective coupling blending technology of varieties of cokes is developed creatively, which increases greatly the supply resource of raw materials for carbon anode manufacturing
(3)The characteristics of Chinese coal tar pitch produced by thermal polymerization process were first studied systematically. The study results show the influences of the solid phases in coal tar pitch, such as mesophase and quinoline insoluble (QI) on the properties of the coke tar pitch. It was found that the coal tar pitch produced by high-temperature thermal polymerization with higher content of toluene insoluble matter, QI and mesophase has a viscosity 3-5 times higher than the one produced by flash distillation process at the same temperatures, which greatly impacts the mixing effect of the paste and the quality of green anodes as well.
(4) The creative integration of coke selective coupling blending technology, new dry aggregates formulation technology, ball milling particle size online analysis technology, butt cleaning and large size particle butt formulation technology, new mixing technology of the pitch from thermal polymerization process and homogenization anode baking technology developed the packaged key-technologies for producing high quality prebaked anodes. And the engineering application was obtained, which made significant economic, social and environmental benefits.
(1)首次系统研究了我国石油焦性质的地域分布特征,结果表明,东北部所产石油焦,硫、钒含量较低,是生产炭阳极产品的优质原料,但量少价高,对生产铝用炭阳极不具经济性；华北、华中地区的炼油厂部分掺配了进口原油,所产石油焦钒、硫含量比使用国产原油生产的石油焦要高得多,且钙含量也普遍较高；华南地区的炼油厂主要使用进口原油生产石油焦,所产石油焦中的硫、钒含量很高,但钙、铁含量较低。
(2)系统研究了我国石油焦特性与炭阳极质量的关联度,揭示了石油焦中微量元素之间的耦合作用行为及其对炭的氧化催化和反催化的影响规律；在此基础上创造性地开发了石油焦选择性耦合混配均质化技术,拓宽了铝用炭阳极的可利用资源。
(3)首次系统研究了我国采用热聚法生产煤沥青的特性,揭示了中间相以及QI等固体相对煤沥青性质的影响规律,结果表明,高温热聚法生产的煤沥青中甲苯不溶物、喹啉不溶物以及中间相含量较高,相同温度下的粘度比闪蒸法生产的煤沥青高3-5倍,对混捏效果和生阳极质量均造成负面影响。
(4)首次将石油焦选择性耦合混配均质化技术、干料配方新技术、球磨粉在线监测及控制技术、残极清理及大颗粒洁净残极配方技术、热聚法煤沥青的混捏新技术、高温均质化焙烧技术等创新集成,形成了优质阳极制备成套关键技术,并成功实现了工程化应用,取得了显著的经济、社会和环境效益。
Anode quality plays an important role for the performance of aluminum smelting cells. Therefore, the thorough study on the production process characteristics and fundamental theories and key-technology development for producing high quality prebaked anodes become an important and urgent research project for Chinese aluminum industry. Focusing on the regionalism and production characteristics of aluminiun-consuming anode coke and coal tar pitch, this paper carried out a fundamental research systematically. And combining with Chinese carbon anode production practice, series of process optimization and engineering technological innovation research were carried out. The theoretical and applied research results were obtained as follow:
(1) A study on the regional distribution characteristics of the properties of Chinese domestic petroleum coke was first systematically carried out. The study results showed that the petroleum coke produced by northeast, with a lower content of S and V element, is the high-quality raw material for carbon anode production. However, it is of low amount and high price, and non-economic for anode production. Refinery in north and central China, which used import crude oil partly, produced petroleum coke with a higher content of V, S and Ca than those produced with domestic crude oil. Refinery in south China mainly used import crude oil and produced petroleum coke with high S, V content, and low Ca, Fe content.
(2) The relation between the characteristics of cokes and carbon anode qualities in our country were studied comprehensively. The study results revealed the coupling effects behavior of the microelements in cokes and their influences of the catalysis and inhibition on carbon oxidation. Based on the study results, a selective coupling blending technology of varieties of cokes is developed creatively, which increases greatly the supply resource of raw materials for carbon anode manufacturing
(3)The characteristics of Chinese coal tar pitch produced by thermal polymerization process were first studied systematically. The study results show the influences of the solid phases in coal tar pitch, such as mesophase and quinoline insoluble (QI) on the properties of the coke tar pitch. It was found that the coal tar pitch produced by high-temperature thermal polymerization with higher content of toluene insoluble matter, QI and mesophase has a viscosity 3-5 times higher than the one produced by flash distillation process at the same temperatures, which greatly impacts the mixing effect of the paste and the quality of green anodes as well.
(4) The creative integration of coke selective coupling blending technology, new dry aggregates formulation technology, ball milling particle size online analysis technology, butt cleaning and large size particle butt formulation technology, new mixing technology of the pitch from thermal polymerization process and homogenization anode baking technology developed the packaged key-technologies for producing high quality prebaked anodes. And the engineering application was obtained, which made significant economic, social and environmental benefits.
引文
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