CN1683597A - Graphitic cathode carbon block for aluminium electrolytic bath and its producing method - Google Patents

Graphitic cathode carbon block for aluminium electrolytic bath and its producing method Download PDF

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Publication number
CN1683597A
CN1683597A CN 200410026089 CN200410026089A CN1683597A CN 1683597 A CN1683597 A CN 1683597A CN 200410026089 CN200410026089 CN 200410026089 CN 200410026089 A CN200410026089 A CN 200410026089A CN 1683597 A CN1683597 A CN 1683597A
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Prior art keywords
carbon block
cathode carbon
weight percent
graphitized cathode
aluminum cell
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CN 200410026089
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CN100350077C (en
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齐仲辉
陈杰
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Fangda Carbon New Materials Technology Co., Ltd.
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HAILONG NEW MATERIAL SCIENCE AND TECHNOLOGY Co Ltd LANZHOU
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Abstract

The graphitized cathode carbon block for aluminum electrolytic bath is prepared with material comprising binder 21-25 wt%, petroleum coke and/or asphalt coke 73-77 wt%, Fe2O3 powder 0.5-1.5 wt% and stearic acid 0.5-1.5 wt%, and through graphitizing treatment. The graphitized cathode carbon block has thermal conductivity coefficient as high as 80 W/m.K, and is favorable to heat dissipation of electrolytic bath bottom and especially suitable for use as cathode lining of large electrolytic bath. The graphitized cathode carbon block has electric resistivity lower than 14 microohm.m and is favorable to lowering cathode voltage drop and saving electric energy. In addition, the graphitized cathode carbon block has low electrolytic expansion rate and high electrolyte corrosion resistance and is favorable to prolonging the service life of electrolytic bath.

Description

Graphitized cathode carbon block for aluminum cell and manufacture method thereof
Technical field:
The present invention relates to graphitized cathode carbon block for aluminum cell.
Background technology:
Aluminium cell is the main equipment in the aluminium refining industry, and build by laying bricks or stones with the charcoal piece usually at its bottom land negative electrode position.Popular cathode carbon pieces kind mainly contains conventional cathode charcoal piece and semi-graphite cathode carbon block in the market.Conventional cathode charcoal piece is to forge hard coal (rotary kiln or pot furnace calcining with general, calcining temperature is about 1300 ℃) for main material production, because its calcining temperature is low, the conventional cathode charcoal piece resistivity of making thus is higher, electrolytic expansivity is very high, corroded by ionogen, and the early damage of electrolyzer takes place, at present except that the small-sized electrolyzer of minority still using, big-and-middle-sized electrolyzer has not re-used conventional cathode charcoal piece.Semi-graphite cathode carbon block is with electric forging coal (electric forge furnace calcining, calcining temperature is between 1200~2000 ℃, average calcining temperature is 1700 ℃) for main material production, with the general coal facies ratio of forging, the calcining degree of depth of electric forging coal increases, and is corresponding therewith, the also corresponding raising of the performance of semi-graphite cathode carbon block, but owing to the thermograde that exists in the electric forge furnace radially, electric forging coal calcining quality is even inadequately, has influenced charcoal piece use properties.In order to solve this type of problem, many producers have added graphite in the semi-graphite cathode carbon block batching, further improved the performance of semi-graphite cathode carbon block thus.But when the graphite addition surpassed 50%, the charcoal piece can produce a large amount of layering waste products in roasting process, say it is infeasible from the angle of economy.Conventional cathode charcoal piece and semi-graphite cathode carbon block are all without greying, because the restriction on this technological process, charcoal piece performance can not obtain breakthrough raising.In addition, along with the maximization day by day of electrolyzer, current density and intensity improve constantly, and accumulate heat in the electrolyzer easily, and in order to strengthen heat radiation, the cell lining material requirements has very high thermal conductivity, need build by laying bricks or stones with graphited carbon material.
Summary of the invention:
The objective of the invention is to avoid the deficiencies in the prior art part and a kind of graphitized cathode carbon block for aluminum cell and manufacture method thereof are provided.This graphitized cathode carbon block for aluminum cell that provides, its resistivity<14 μ Ω .m, thermal conductivity>80W/m.K (room temperature), electrolytic expansivity<0.15%.This charcoal piece is particularly suitable for the cathode inner lining of large scale electrolytic cell.
Purpose of the present invention can be by realizing by the following technical solutions: a kind of graphitized cathode carbon block for aluminum cell, its proportioning raw materials (weight percent) include binding agent 21~25%, refinery coke or and pitch coke 73~77%, Fe 2O 3Powder 0.5~1.5%, stearic acid 0.5~1.5%.
Use Fe among the present invention 2O 3Powder is in order to prevent that goods from inflatable taking place in graphitizing process; Using stearic acid is in order to improve the plasticity of thickener.
Described graphitized cathode carbon block for aluminum cell, siccative size composition (weight percent) are that 6~4mm is 10~32%; 4~1mm is 20~26%; 1~0.15mm is 13~19%; ≤ 0.15mm is 35~45%.
Siccative is not for comprising other raw material of binding agent.
Described binding agent is a coal-tar pitch.
The manufacture method of graphitized cathode carbon block for aluminum cell of the present invention includes:
(1). pulverize;
(2). screening: by its sizing;
(3). batching:
B. by its proportioning raw materials (weight percent) binding agent 21~25%, refinery coke or and pitch coke 73~77%, Fe 2O 3Powder 0.5~1.5%, stearic acid 0.5~1.5%.
B. by its siccative size composition (weight percent) be: be that 6~4mm is 10~32%; 4~1mm is 20~26%; 1~0.15mm is 13~19%; ≤ 0.15mm is 35~45%.
(4). mix and pinch; Major equipment uses kneading machine.
(5). cool material;
(6). extrusion molding;
(7). roasting: at holding-zone, temperature reaches 1350-1410 ℃, and soaking time is 10-20 hour;
(8). dipping; In dipping is irritated, add coal-tar pitch; Pressure is 1.2-1.8MP, keeps 1-4 hour, fills nitrogen.
(9). two burn; Re-baking, temperature reach 800-900 ℃, and soaking time is 8-13 hour.
(10). inner bunch graphitization; In inner string graphitization stove, finish.
(11). mechanical workout.
The manufacture method of described graphitized cathode carbon block for aluminum cell also includes:
(8). inner bunch graphitization;
(9). dipping; In dipping is irritated, add coal-tar pitch; Pressure is 1.2-1.8MP, keeps 1-4 hour, fills nitrogen.
(10). two burn.Re-baking, temperature reach 800-900 ℃, and soaking time is 8-13 hour.
In existing manufacturing cathode carbon pieces technology, be not comprise operations such as inner bunch graphitization, dipping, two burnings.The present invention has adopted dipping, two firing techniques for improving the density and the intensity of charcoal piece.Wherein steeping fluid is mainly coal-tar pitch.Inner bunch graphitization is the serial graphitized technology of internal heat type.
The invention has the beneficial effects as follows,
1, because main raw material has used refinery coke or pitch coke, and through graphitization processing, the graphitized cathode carbon block thermal conductivity helps the bottom land heat radiation up to more than the 80W/m.K, is particularly suitable for the cathode inner lining of large scale electrolytic cell.
2, graphitized cathode carbon block resistivity<14 μ Ω .m, more much lower than conventional cathode charcoal piece and semi-graphite cathode carbon block, help reducing cathode drop, reach energy saving purposes.
3, the graphitized cathode carbon block electrolytic expansivity is low, the potential resistance to electrolyte contamination erosion performance is good, helps prolonging the life-span of electrolyzer.
Embodiment:
Be described in further detail in conjunction with embodiment shown below:
Embodiment 1:
Graphitized cathode carbon block for aluminum cell, its proportioning raw materials (weight percent) coal-tar pitch 23%, refinery coke 75%, Fe 2O 3Powder 0.5%, stearic acid 1.5%.
Siccative size composition (weight percent) is that 6~4mm is 20%; 4~1mm is 25%; 1~0.15mm is 15%; ≤ 0.15mm is 40%.
Embodiment 2:
Graphitized cathode carbon block for aluminum cell, its proportioning raw materials (weight percent) coal-tar pitch 25%, pitch coke 73%, Fe 2O 3Powder 1.5%, stearic acid 0.5%.
Siccative size composition (weight percent) is that 6~4mm is 10%; 4~1mm is 26%; 1~0.15mm is 19%; ≤ 0.15mm is 45%.
Embodiment 3:
Graphitized cathode carbon block for aluminum cell, its proportioning raw materials (weight percent) coal-tar pitch 21%, refinery coke and pitch coke (1: 1) 77%, Fe 2O 3Powder 1%, stearic acid 1%.
Siccative size composition (weight percent) is that 6~4mm is 32%; 4~1mm is 20%; 1~0.15mm is 13%; ≤ 0.15mm is 35%.
Embodiment 4:
The manufacture method of described graphitized cathode carbon block for aluminum cell includes:
(1). pulverize;
(2). screening: by its sizing;
(3). batching:
A. by its proportioning raw materials (weight percent) binding agent 21~25%, refinery coke or pitch coke 73~77%, Fe 2O 3Powder 0.5~1.5%, stearic acid are 0.5~1.5%.
B. by its siccative size composition (weight percent) be: be that 6~4mm is 10~32%; 4~1mm is 20~26%; 1~0.15mm is 13~19%; ≤ 0.15mm is 35~45%.
(4). mix and pinch; Major equipment uses kneading machine.
(5). cool material;
(6). extrusion molding;
(7). roasting: at holding-zone, temperature reaches 1350-1410 ℃, and soaking time is 10-20 hour;
(8). dipping; In dipping is irritated, add coal-tar pitch; Pressure is 1.2-1.8MP, keeps 1-4 hour, fills nitrogen.
(9). two burn; Re-baking, temperature reach 800-900 ℃, and soaking time is 8-13 hour.
(10). inner bunch graphitization;
(11). mechanical workout.
Embodiment 5:
The manufacture method of described graphitized cathode carbon block for aluminum cell includes:
(1). pulverize;
(2). screening: by its sizing;
(3). batching:
A. by its proportioning raw materials (weight percent) binding agent 21~25%, refinery coke or pitch coke 73~77%, Fe 2O 3Powder 0.5~1.5%, stearic acid 0.5~1.5%.
B. by its siccative size composition (weight percent) be: be that 6~4mm is 10~32%; 4~1mm is 20~26%; 1~0.15mm is 13~19%; ≤ 0.15mm is 35~45%.
(4). mix and pinch; Major equipment uses kneading machine.
(5). cool material;
(6). extrusion molding;
(7). roasting: at holding-zone, temperature reaches 1350-1410 ℃, and soaking time is 10-20 hour;
(8). inner bunch graphitization;
(9). dipping; In dipping is irritated, add coal-tar pitch; Pressure is 1.2-1.8MP, keeps 4 hours, fills nitrogen.
(10). two burn; Re-baking, temperature reach 800-900 ℃, and soaking time is 8 hours.
(11). mechanical workout.
It detects index such as following table by above-mentioned enforcement:
The present invention is through implementing the tabulation of its physical and chemical index and like product contrast situation
Sequence number Index name Unit Conventional cathode charcoal piece Semi-graphite cathode carbon block Graphitized cathode carbon block
??1 Ash content ??% ??≤9 ??≤7 ??≤0.3
??2 True density ??g/cm 3 ??≥1.86 ??≥1.90 ??≥2.18
??3 Volume density ??g/cm 3 ??≥1.54 ??≥1.56 ??≥1.62
??4 True porosity ??% ??≤26
??5 Compressive strength ??MPa ??≥32 ??≥32 ??≥30
??6 Folding strength ??MPa ??≥8
??7 Compare resistance ??μΩ.m ??≤55 ??≤40 ??≤14
??8 Electrolytic expansivity ??% ??≤1.0 ??≤0.15
??9 Damage coefficient ??≤1.5
??10 Thermal conductivity (room temperature) ??W/m.K ??≥80.
From table, can find out than resistance<14 μ Ω .m; Thermal conductivity is up to more than the 80W/m.K, and effect is very remarkable.

Claims (5)

1. graphitized cathode carbon block for aluminum cell, its proportioning raw materials (weight percent) includes binding agent 21~25%, refinery coke Huo and pitch coke 73~77%, Fe 2O 3Powder 0.5~1.5%, stearic acid 0.5~1.5%.
2. graphitized cathode carbon block for aluminum cell as claimed in claim 1, it is characterized in that also including siccative size composition (weight percent) is that 6~4mm is 10~32%; 4~1mm is 20~26%; 1~0.15mm13~19%; ≤ 0.15mm is 35~45%.
3. as claim 1 and 2 described graphitized cathode carbon block for aluminum cell, it is characterized in that binding agent is a coal-tar pitch.
4. as the manufacture method of claim 1 and 2 described graphitized cathode carbon block for aluminum cell, include:
(1). pulverize;
(2). screening: by its sizing;
(3). batching:
A. by its proportioning raw materials (weight percent) binding agent 21~25%, refinery coke or pitch coke 73~77%, Fe 2O 3Powder is 0.5~1.5%, stearic acid is 0.5~1.5%.
B. by its siccative size composition (weight percent) be: be that 6~4mm is 10~32%; 4~1mm is 20~26%; 1~0.15mm is 13~19%; ≤ 0.15mm is 35~45%.
(4). mix and pinch; Major equipment uses kneading machine.
(5). cool material;
(6). extrusion molding;
(7). roasting: at holding-zone, temperature reaches 1350-1410 ℃, and soaking time is 10-20 hour;
(8). dipping; In dipping is irritated, add coal-tar pitch; Pressure is 1.2-1.8MP, keeps 1-4 hour, fills nitrogen.
(9). two burn; Re-baking, temperature reach 800-900 ℃, and soaking time is 8-13 hour.
(10). inner bunch graphitization; In inner string graphitization stove, finish.
(11). mechanical workout.
5. the manufacture method of graphitized cathode carbon block for aluminum cell as claimed in claim 4 also includes: wherein be
(8). inner bunch graphitization;
(9). dipping;
(10). two burn.
CNB2004100260895A 2004-04-15 2004-04-15 Graphitic cathode carbon block for aluminium electrolytic bath and its producing method Expired - Fee Related CN100350077C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100457681C (en) * 2006-11-07 2009-02-04 中钢集团吉林炭素股份有限公司 High conductive high strength graphite brick for ultralarge blast furnace, its production technology and application
CN101665957B (en) * 2009-09-23 2011-01-12 四川广汉士达炭素股份有限公司 Anti-abrasion graphitization cathode carbon blocks used for aluminum electrolytic cell and manufacturing method thereof
CN102158999A (en) * 2011-05-16 2011-08-17 方大炭素新材料科技股份有限公司 Phi 800mm general power graphite electrode and production method thereof
CN102674853A (en) * 2012-05-15 2012-09-19 河南方圆炭素集团有限公司 Graphite core for nickel iron electric furnace door
CN103374729A (en) * 2012-04-17 2013-10-30 夏华松 Production process of high-purity graphite cathode
CN104129782A (en) * 2014-07-30 2014-11-05 焦作市中州炭素有限责任公司 Graphite electrode with diameter of 348 mm and manufacture method thereof
CN108218429A (en) * 2017-10-10 2018-06-29 中国矿业大学 A kind of method that high purity graphite material is prepared using coal tar pitch as raw material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000086343A (en) * 1998-09-09 2000-03-28 Sec Corp Carbon composite material and its production
US20020000373A1 (en) * 2000-05-22 2002-01-03 Hirofumi Ninomiya Graphitized cathode block for aluminum smelting
JP2002266091A (en) * 2001-03-09 2002-09-18 Sec Corp Graphit cathode block for smelting aluminum
CN1229523C (en) * 2003-09-02 2005-11-30 中国铝业股份有限公司 Process for producing cathode carbon block for aluminum cell

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100457681C (en) * 2006-11-07 2009-02-04 中钢集团吉林炭素股份有限公司 High conductive high strength graphite brick for ultralarge blast furnace, its production technology and application
CN101665957B (en) * 2009-09-23 2011-01-12 四川广汉士达炭素股份有限公司 Anti-abrasion graphitization cathode carbon blocks used for aluminum electrolytic cell and manufacturing method thereof
CN102158999A (en) * 2011-05-16 2011-08-17 方大炭素新材料科技股份有限公司 Phi 800mm general power graphite electrode and production method thereof
CN103374729A (en) * 2012-04-17 2013-10-30 夏华松 Production process of high-purity graphite cathode
CN102674853A (en) * 2012-05-15 2012-09-19 河南方圆炭素集团有限公司 Graphite core for nickel iron electric furnace door
CN102674853B (en) * 2012-05-15 2013-09-04 河南方圆炭素集团有限公司 Graphite core for nickel iron electric furnace door
CN104129782A (en) * 2014-07-30 2014-11-05 焦作市中州炭素有限责任公司 Graphite electrode with diameter of 348 mm and manufacture method thereof
CN108218429A (en) * 2017-10-10 2018-06-29 中国矿业大学 A kind of method that high purity graphite material is prepared using coal tar pitch as raw material

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