WO2008046255A1 - Procédé de production de blocs de carbone de cathode mouillable - Google Patents

Procédé de production de blocs de carbone de cathode mouillable Download PDF

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Publication number
WO2008046255A1
WO2008046255A1 PCT/CN2006/003315 CN2006003315W WO2008046255A1 WO 2008046255 A1 WO2008046255 A1 WO 2008046255A1 CN 2006003315 W CN2006003315 W CN 2006003315W WO 2008046255 A1 WO2008046255 A1 WO 2008046255A1
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titanium boride
cathode
composite
carbon
carbon blocks
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PCT/CN2006/003315
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English (en)
French (fr)
Inventor
Fengqin Liu
Hongjie Yang
Kaibin Chen
Yingtao Luo
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Aluminum Corporation Of China Limited
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Priority to DE112006004078T priority Critical patent/DE112006004078B4/de
Publication of WO2008046255A1 publication Critical patent/WO2008046255A1/zh

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08Cell construction, e.g. bottoms, walls, cathodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B30PRESSES
    • B30BPRESSES IN GENERAL
    • B30B11/00Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
    • B30B11/02Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses using a ram exerting pressure on the material in a moulding space
    • B30B11/022Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses using a ram exerting pressure on the material in a moulding space whereby the material is subjected to vibrations

Definitions

  • the invention relates to a method for preparing a wettable cathode carbon block, relating to a wet cathode carbon block used in an aluminum electrolysis process, in particular to a production method of a flow-off cathode carbon block for a flow-through electrolyzer.
  • the diversion electrolyzer technology is currently the most viable technology to achieve a significant reduction in the electricity consumption per ton of aluminum without changing the Hall-Erre electrolysis process.
  • the most critical technology for the flow-through type electrolytic cell is to research and develop a cathode carbon block that has better wettability with aluminum liquid, long-term resistance to cryolite corrosion, and no deformation.
  • the use of integrated vibration molding technology to produce titanium boride-graphite composite layer can wet the performance of cathode carbon block, which is superior to the performance of titanium boride coating technology commonly used in the world.
  • the use of integrated vibration molding technology to produce titanium boride-graphite composite layer wet cathode carbon block has been successfully applied in different specifications of electrolytic cells. At the initial stage of the electrolysis cell startup, the infiltration amount of the cryolite electrolyte is significantly reduced, the furnace bottom pressure is lowered and the operation is stable during the electrolysis production process, and the life of the electrolytic cell is obviously improved.
  • the titanium boride-graphite composite layer is required to have a high content of titanium boride, and the thickness of the composite layer can satisfy the surface of the cathode. Or the need to have a working face with a 2 - 15 degree tilt angle.
  • the fine-grained titanium boride powder is used as the source of titanium boride, which limits the thickness and composite of the composite layer. An increase in the content of titanium boride in the layer. This is due to the excessive amount of powder, which leads to the unreasonable formulation of the composite layer paste.
  • the thickness of the composite layer of the wettable cathode carbon block produced is not ideal, and the content of titanium boride in the composite layer is low, which cannot meet the requirements of the conductivity type electrolytic cell.
  • the object of the present invention is to provide an anti-cryolite electrolyte erosion, a small deformation, a groove on the working surface, or a working surface with a tilt angle of 2 - 15 degrees, in view of the deficiencies of the prior art described above.
  • a method for preparing a wettable cathode carbon block comprising: a compounding, a vibration molding of a cathode substrate, a vibration forming and sintering process of a composite layer on a cathode substrate; wherein the compounding of the composite layer on the cathode substrate is added during the preparation process
  • the titanium boride is added in the form of a particulate titanium boride carbon composite.
  • the invention provides a method for preparing a wettable cathode carbon block, characterized in that the weight content of titanium boride in the granular titanium boride carbon composite material is 80%.
  • the titanium boride carbon composite bulk material produced by the method of the invention is produced by using artificial graphite material, titanium boride powder as dry material, coal tar pitch as binder, and common carbon material production method, by kneading, molding, The roasting process is made.
  • the invention provides a preparation method of a wettable cathode carbon block, characterized in that the weight composition of the composite layer paste is: titanium boride carbon composite material with a particle size of 6 - 3 mm: 16 - 30%; particle size is 3 - 0 mm Titanium boride carbon composite: 10 - 20%; graphite broken 3 - 0mm 10 - 15%, titanium boride powder: 10 - 40%; coal pitch is 18 - 23%.
  • a titanium boride carbon composite block material is used as the aggregate, and the titanium boride component in the composite layer paste is added in the form of particles and fine powder, thereby overcoming the composite layer produced by using only the titanium boride powder.
  • the carbon block produces a large number of crack defects in the composite layer after calcination, effectively increasing the content of titanium boride in the composite layer, and the thickness of the composite layer can reach 20 - 200 mm.
  • the cathode surface is inclined. , the production of grooved shaped cathode carbon blocks.
  • the working surface of the carbon block can be grooved or the working if has a tilt angle of 2 - 15 degrees; It has the characteristics of anti-cryolite electrolyte erosion and small deformation, and can be used as a drain type for the flow guiding type electrolytic cell.
  • Cathode carbon block It satisfies the requirement that the working surface of the carbon block can be grooved or the working if has a tilt angle of 2 - 15 degrees; It has the characteristics of anti-cryolite electrolyte erosion and small deformation, and can be used as a drain type for the flow guiding type electrolytic cell. Cathode carbon block.
  • a method for preparing a wettable cathode carbon block comprising: compounding, vibration molding of a cathode substrate, vibration forming and sintering process of a composite layer on a cathode substrate; boron added during compounding of a layer composite on a cathode substrate during preparation Titanium is added in the form of a granular titanium boride carbon composite.
  • the weight content of titanium boride in the granular titanium boride carbon composite material is 80%.
  • the weight composition of the composite layer paste is: titanium boride carbon composite material having a particle size of 6 - 3 mm: 16 - 30%; titanium boride carbon material having a particle size of 3 - 0 mm: 10 - 20%; graphite broken 3 - 0 mm 10 - 15%, titanium boride powder: 10 - 40%; coal pitch is 18 - 23%.
  • Example 1 titanium boride carbon composite material having a particle size of 6 - 3 mm: 16 - 30%; titanium boride carbon material having a particle size of 3 - 0 mm: 10 - 20%; graphite broken 3 - 0 mm 10 - 15%, titanium boride powder: 10 - 40%; coal pitch is 18 - 23%.
  • the kettle with 100L of heat medium (or electric heating), use 50% by weight of titanium boride carbon composite, 33 % graphite, dry mixing time 20 - 30 min. After mixing dry ingredients, add melted good softening point 105 ⁇ liquid modified asphalt mass ratio of 17%, subjected to wet mixing, kneading temperature 160 - 1 7 0 ° C, time 40 - 5 0min.
  • the titanium boride carbon composite material having a particle size of 6 - 3 mm: 25%; the particle size is 0 - 3 mm, the titanium boride carbon composite material: 30%; the titanium boride powder: 40%; 0mm 5%.
  • the amount of coal pitch in the paste is 20%.
  • the base material is a paste for producing a cathode carbon block using an electrically calcined anthracite as an aggregate (having a powder resistivity of 550 ⁇ ⁇ ).
  • Weigh 1450Kg of cathode matrix paste add weight to the mold in the length of 3620mm and 560mm and vibrate for 45sec. Lift the weight and pull the surface with special tools. Spread the composite 80Kg, and then put down the weight and vibrate for 2min. Support, cooling. After 230h heating and roasting, it is baked, processed and inspected.
  • the composite layer is tightly integrated with the substrate. It has no obvious interface. Its thickness is 24mm. It has no cracking and no layering. It can be completely wetted with metal aluminum liquid after testing.
  • Example 2 The other parameters were the same as in Example 1, in which 50 L of hot medium (or electric heating) was used to knead the pot, and the weight ratio of the total batching was 70% of the titanium boride carbon composite and 13% of the graphite crumb.
  • the composite layer pastes the titanium boride carbon composite material having a particle size of 6 - 3 mm: 16%; the titanium boride carbon material composite material having a particle size of 0 - 3 mm: 31%; the titanium boride powder: 40%; 0mm 13%; the amount of coal pitch in the paste is 22%.
  • the composite layer paste is then added 29. 5 Kg,, paste coated on the substrate, using the ram novel structure, vibration After 3 minutes, the mold was released, and a cathode carbon block having a green body of 3300 x 545 X 470 mm and a working surface inclination angle of 4 degrees was obtained, which was cooled, calcined, machined, and inspected.
  • the composite layer is integrated with the substrate, has no obvious interface, and the working surface is flat.
  • the thickness of the composite layer is about 10 mm, which can be completely wetted with the metal aluminum solution after testing.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)

Description

一种可湿润阴极炭块的制备方法 技术领域
一种可湿润阴极炭块的制备方法, 涉及铝电解过程使用的可 湿润阴极炭块, 特别是适用于导流式电解槽用泄流式阴极炭块的 生产方法。
背景技术
导流式电解槽技术是目前在不改变霍尔 -埃鲁尔电解工艺的 前提下, 能够实现大幅度降低吨铝电耗的最可行的技术。 导流式 电解槽最关键的技术是要研究、 开发出与铝液湿润性更好、 长期 抗冰晶石电解质侵蚀、 不变形的阴极炭块。
目前, 釆用一体化振动成型技术生产硼化钛-石墨复合层可 湿润阴极炭块的性能, 优于国际上普遍采用的硼化钛涂层技术生 产的性能。 采用一体化振动成型技术生产硼化钛 -石墨复合层可 湿润阴极炭块在不同规格电解槽上得到了成功应用。 在电解槽启 动初期, 冰晶石电解质渗入量明显減少、 电解生产过程中炉底压 降低且运行稳定, 明显提高了电解槽的寿命。
但是, 由于导流式电解槽需要湿润性更好、 抗腐蚀能力更强 的阴极炭块, 要求硼化钛-石墨复合层中硼化钛含量高, 复合层的 厚度能满足阴极表面开沟槽或者使工作面带有 2 - 15 度倾斜角的 需求。 在目前的一体化振动成型技术生产硼化钛-石墨复合层可湿 润阴极炭块的生产过程中, 是采用粒度较细的硼化钛粉末作为硼 化钛的来源, 限制了复合层厚度及复合层中硼化钛含量的增加。 这是由于粉料过多, 导致复合层糊料配方的不合理, 振动成型的 炭块在焙烧后, 会造成复合层产生大量裂纹。 使生产的可湿润阴 极炭块复合层厚度不理想, 复合层中硼化钛含量低, 不能满足导 流式电解槽的要求。
发明内容
本发明的目的在于针对上述已有技术存在的不足, 提供一种 能够生产出抗冰晶石电解质侵蚀、 变形小、 工作面上可开沟槽或 者使工作面带有 2 - 15 度倾斜角, 满足导流式电解槽对湿润性要 求的阴极材料的可湿润阴极炭块的制备方法。 本发明的目的是通过以下技术方案实现的。
一种可湿润阴极炭块的制备方法, 包括配料、 阴极基体振动 成型、 在阴极基体上复合层料振动成型和烧结过程; 其特征在于 制备过程中在阴极基体上的复合层料的配料时加入的硼化钛是以 颗粒状的硼化钛炭复合材料形式加入的。
本发明提供一种可湿润阴极炭块的制备方法, 其特征在于颗 粒状硼化钛炭复合材料中硼化钛重量含量为 80%。
本发明方法的硼化钛炭复合块状材料的生产, 是以人造石墨 材料、 硼化钛粉为干料, 用煤沥青做粘结剂, 应用普通炭素材料 的生产方法, 通过混捏、 成型、 焙烧过程制得。
本发明提供一种可湿润阴极炭块的制备方法, 其特征在于其 复合层糊料的重量组成为: 粒度为 6 - 3mm的硼化钛炭复合材料: 16 - 30%; 粒度为 3 - 0mm 硼化钛炭复合材料: 10 - 20%; 石墨 碎 3 - 0mm 10 - 15% , 硼化钛粉: 10 - 40%; 煤沥青为 18 - 23%。
本发明的方法, 采用硼化钛炭复合块状材料作为骨料, 复合 层糊料中硼化钛成份以颗粒、 细粉两种形式加入, 克服了只使用 硼化钛粉料生产的复合层炭块在焙烧后复合层产生大量裂纹的缺 陷, 有效提高了复合层中硼化钛的含量, 复合层厚度可达 20 - 200mm , 通过改变成型模具上压头的形状, 实现阴极表面带倾斜 角、 沟槽的异型阴极炭块的生产。 满足了在炭块工作面上可开沟 槽的或者使工作 if带有 2 - 15 度倾斜角的要求; 具有抗冰晶石电 解质侵蚀、 变形小特点, 可作为导流式电解槽用泄流式阴极炭块。
具体实施方式
一种可湿润阴极炭块的制备方法, 包括配料、 阴极基体振动 成型、 在阴极基体上复合层料振动成型和烧结过程; 制备过程中 的在阴极基体上复合的层料的配料时加入的硼化钛是以颗粒状的 硼化钛炭复合材料形式加入的。 其中颗粒状硼化钛炭复合材料中 硼化钛重量含量为 80%。 其复合层糊料的重量组成为: 粒度为 6 - 3mm 的硼化钛炭复合材料: 16 - 30%; 粒度为 3 - 0mm硼化钛 炭复合材料: 10 - 20%; 石墨碎 3 - 0mm 10 - 15% , 硼化钛粉: 10 - 40%; 煤沥青为 18 - 23%。 实施例 1
用 100L 热媒 (或电加热) 混捏锅, 使用重量 50%的硼化钛 炭复合材料、 33%石墨碎, 干混时间 20 - 30min。 待干料混匀后, 加入溶化好的软化点是 105Ό液体改质沥青, 质量比 17% , 进行 湿混, 混捏温度 160 - 170°C, 时间 40 - 50min。 其中复合层糊料 中, 粒度为 6 - 3mm的硼化钛炭复合材料: 25%; 粒度为 0- 3mm 硼化钛炭复合材料: 30%; 硼化钛粉: 40%; 石墨碎 3- 0mm 5%。 糊料中煤沥青用量 20%。
基体料为以电煅无烟煤为骨料 (其粉末电阻率为 550 μ Ωιη) 的阴极炭块生产用糊料。称取阴极基体糊料 1450Kg,在长 3620mm 宽 560mm 的模箱中加重锤并振动 45sec, 提起重锤, 用专用工具 将表面拉毛, 均勾铺上复合料 80Kg, 重新放下重锤并振动 2min 后托模、 冷却。 经 230h 加热焙烧后出炉、 加工、 检查, 复合层 与基体紧密融为一体, 无明显界面, 其厚度为 24mm, 无开裂、 无起层, 经试验可与金属铝液完全润湿。 实施例 1
其它参数与例 1相同, 其中用 50L热媒 (或电加热) 混捏锅, 将重总配料重量比为 70%的硼化钛炭复合材料、 13%的石墨碎配 料。 其中复合层糊料中, 粒度为 6- 3mm 的硼化钛炭复合材料: 16%; 粒度为 0- 3mm硼化钛炭复合材料: 31%; 硼化钛粉: 40%; 石墨碎 3- 0mm 13%; 糊料中煤沥青用量 22%。
先在 3300 x 545mm的模箱中均勾平铺已经混捏好的基体糊料 1320Kg, 然后加入复合层糊料 29.5Kg, , 覆盖在基体糊料上, 使 用新型结构的上压头, 振动 3min后脱模, ,得到生坯为 3300 x 545 X 470mm, 工作面倾斜角为 4 度的阴极炭块, 经冷却、 焙烧、 机 加、 检查。 复合层与基体形成一体, 无明显界面, 工作面平整, 复合层厚度约 10mm, 经试验可与金属铝液完全润湿。

Claims

权 利 要 求
1. 一种可湿润阴极炭块的制备方法, 包括配料、 阴极基体 振动成型、 在阴极基体上复合层料振动成型和烧结过程; 其特征 在于制备过程中的在阴极基体上复合的层料的配料时加入的硼化 钛是以颗粒状的硼化钛炭复合材料形式加入的。
2. 根据权利要求 1 所述的一种可湿润阴极炭块的制备方法, 其特征在于其中颗粒状硼化钛炭复合材料中硼化钛重量含量为 80%。
3. 根据权利要求 1 所述的一种可湿润阴极炭块的制备方法, 其特征在于硼化钛炭复合材料的生产, 是以人造石墨材料、 硼化 钛粉为干料, 用煤沥青做粘结剂, 应用普通炭素材料的生产方法, 通过混捏、 成型、 焙烧过程制得。
4. 根据权利要求 1 所述的一种可湿润阴极炭块的制备方法, 其特征在于其硼化钛炭复合材料层糊料的重量组成为: 粒度为 6 - 3mm 的硼化钛炭复合材料: 16 - 30%; 粒度为 3 - 0mm硼化钛 炭复合材料: 10 - 20%; 石墨碎 3 - 0mm 10 - 15% , 硼化钛粉: 10 - 40%。 糊料中煤沥青为 18 - 23%。
PCT/CN2006/003315 2006-10-18 2006-12-06 Procédé de production de blocs de carbone de cathode mouillable WO2008046255A1 (fr)

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DE102010038650A1 (de) 2010-07-29 2012-02-02 Sgl Carbon Se Verfahren zur Herstellung eines Kathodenblocks für eine Aluminium-Elektrolysezelle und einen Kathodenblock
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CN105780054B (zh) * 2016-04-27 2018-04-20 新疆大学 以铝作为阴极的铝电解槽阴极

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