CN100491600C - Method for preparing carbon block of cathode capable of being humidified - Google Patents
Method for preparing carbon block of cathode capable of being humidified Download PDFInfo
- Publication number
- CN100491600C CN100491600C CNB200610140573XA CN200610140573A CN100491600C CN 100491600 C CN100491600 C CN 100491600C CN B200610140573X A CNB200610140573X A CN B200610140573XA CN 200610140573 A CN200610140573 A CN 200610140573A CN 100491600 C CN100491600 C CN 100491600C
- Authority
- CN
- China
- Prior art keywords
- titanium boride
- cathode
- carbon
- carbon composite
- wetable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010936 titanium Substances 0.000 claims abstract description 60
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 13
- 238000005056 compaction Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 239000011294 coal tar pitch Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000011246 composite particle Substances 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 229910001610 cryolite Inorganic materials 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000011295 pitch Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- 206010011376 Crepitations Diseases 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004826 seaming Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 sodium aluminum fluoride Chemical compound 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B11/00—Presses specially adapted for forming shaped articles from material in particulate or plastic state, e.g. briquetting presses, tabletting presses
- B30B11/02—Presses 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
- B30B11/022—Presses 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
Landscapes
- 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)
Abstract
This invention discloses a method for preparing wettable cathode carbon bloc for aluminum electrolysis, especially drained cathode carbon block used in drained electrolytic cell. The method comprises: mixing the raw materials, molding the cathode matrix by vibration, molding the composite coating layer on the cathode matrix by vibration, and sintering. The composite coating layer is added with granular titanium boride. The method increases titanium boride content in the composite coating layer, and the thickness is up to 20-200 mm. Besides, the method can change the structure of the upper pressure head of the mold is changed, thus realize the production of special shaped carbon block with 2-15 deg. inclined angle or grooves on the cathode carbon block surface. The obtained cathode carbon block has such advantages as good cryolite electrolyte corrosion resistance and small deformation, and can be used as drained cathode carbon block in drained electrolytic cell.
Description
Technical field
A kind of preparation method of wetable cathode carbon piece relates to the wetable cathode carbon piece that aluminium electrolysis process uses, and particularly is applicable to the production method of guide flow type electrolyzer with the drainage type cathode carbon pieces.
Background technology
The guide flow type cell technologies is at present under the prerequisite that does not change Hall-Ai Luer electrolysis process, can realize reducing significantly ton the most feasible technology of aluminium power consumption.The technology of guide flow type electrolyzer most critical is will study, develop and better, the long-term anti-sodium aluminum fluoride ionogen erosion of aluminium liquid wettability, indeformable cathode carbon pieces.
At present, adopt integrated vibratory compaction technology to produce the performance of titanium boride-graphite composite bed wetable cathode carbon piece, the performance that the titanium boride coating technology that is better than generally adopting is in the world produced.Adopt integrated vibratory compaction technology to produce titanium boride-graphite composite bed wetable cathode carbon piece and on the different size electrolyzer, obtained successful Application.At the electrobath start initial stage, sodium aluminum fluoride ionogen infiltration capacity obviously reduces, in the electrolysis production process furnace bottom pressure drop low and stable, the life-span of obviously having improved electrolyzer.
But, because the guide flow type electrolyzer needs the cathode carbon pieces that wettability is better, resistance to corrosion is stronger, require titanium boride content height in titanium boride-graphite composite bed, the thickness of composite bed can satisfy the cathode surface open channels or make working face have the demand at 2-15 degree pitch angle.Produce in the production process of titanium boride-graphite composite bed wetable cathode carbon piece in present integrated vibratory compaction technology, be to adopt the source of the thinner powders of titanium boride of granularity, limited the increase of titanium boride content in composite bed thickness and the composite bed as titanium boride.This is because powder is too much, causes the unreasonable of composite bed paste formula, and the charcoal piece of vibratory compaction can cause composite bed to produce a large amount of crackles after roasting.Make the wetable cathode carbon piece composite bed thickness of production undesirable, titanium boride content is low in the composite bed, can not satisfy the requirement of guide flow type electrolyzer.
Summary of the invention
The objective of the invention is to deficiency at above-mentioned prior art existence, but provide a kind of and can produce that anti-sodium aluminum fluoride ionogen corrodes, distortion is little, open channels or make working face have 2-15 degree pitch angle on the working face, satisfy the preparation method of the wetable cathode carbon piece of the cathode material that the guide flow type electrolyzer requires wettability.
The objective of the invention is to be achieved through the following technical solutions.
A kind of preparation method of wetable cathode carbon piece comprises batching, cathode base vibratory compaction, compound coating layer vibratory compaction and sintering process on cathode base; The titanium boride that adds when it is characterized in that in the preparation process on the cathode base batching of compound coating layer be mix with granular warp pinch, titanium boride carbon composite form that moulding, sintering form adds.
The preparation method of a kind of wetable cathode carbon piece of method of the present invention, the titanium boride weight content that it is characterized in that its particulate state titanium boride carbon composite is 80%.
The production of the titanium boride carbon composite of the inventive method is to be siccative with synthetic graphite material, titanium boride powder, makees binding agent with coal-tar pitch, uses the production method of common carbon material, pinches by mixing, moulding, roasting process make.
The preparation method of a kind of wetable cathode carbon piece of method of the present invention, it is characterized in that the titanium boride part in its titanium boride carbon composite layer thickener adds with titanium boride carbon composite particle form, part adds with the titanium boride powder form, and its siccative weight consists of: granularity is the titanium boride matrix material of 6-3mm: 16%-30%; Granularity is 3-0mm titanium boride carbon composite: 10%-20%; Granularity is the broken 10%-15% of 3-0mm graphite, titanium boride powder: 10%-40%; Coal-tar pitch in the thickener is 18%-23%.
Method of the present invention, adopt the titanium boride matrix material as aggregate, composite bed thickener titanium boride composition adds with particle, two kinds of forms of fine powder, the charcoal piece that has overcome the vibratory compaction of using the generation of titanium boride powder batching is after roasting, composite bed produces the defective of a large amount of crackles, has effectively improved the titanium boride content of composite bed, and composite bed thickness can reach 20-200mm, by changing the shape of forming mould seaming chuck, realize the production of the specially-shaped cathode charcoal piece of cathode surface band pitch angle, groove.But satisfied on charcoal piece working face open channels or make working face have the requirement at 2-15 degree pitch angle; Have anti-sodium aluminum fluoride ionogen and corrode, be out of shape little characteristics, can be used as guide flow type electrolyzer drainage type cathode carbon pieces.
Embodiment
A kind of preparation method of wetable cathode carbon piece comprises batching, cathode base vibratory compaction, compound coating layer vibratory compaction and sintering process on cathode base; The titanium boride that adds during the batching of compound layered material on cathode base in the preparation process adds with granular titanium boride carbon composite form.Wherein the titanium boride weight content of particulate state titanium boride carbon composite is 80%.The weight of its titanium boride carbon composite layer thickener consists of: granularity is the titanium boride carbon composite of 6-3mm: 16%-30%; Granularity is 3-0mm titanium boride carbon composite: 10%-20%; Granularity is the broken 10%-15% of being of 3-0mm graphite, titanium boride powder: 10%-40%; Coal-tar pitch is 18%-23%.
Embodiment 1
With the mixed pot of pinching of 100L heating agent (or electrically heated), matrix material, the broken mixing of 33% graphite that will account for batching gross weight titanium boride 50%, the dried 20～30min that does time.After treating the siccative mixing, adding the softening temperature that dissolves for liquid is 105 ℃ of modified pitch mass ratioes 17%, carries out wet mixing, 160～170 ℃ of kneading temperatures, time 40～50min.Wherein titanium boride carbon composite mass ratio is: granularity is the titanium boride carbon composite of 6-3mm: 25%; Granularity is a 0-3mm titanium boride carbon composite: 30%; Titanium boride powder: 40%; Broken 3-the 0mm 5% of graphite.Coal-tar pitch consumption 20% in the thickener.
The matrix material is for being the cathode carbon pieces production thickener of aggregate (its powder resistivity is 550 μ Ω m) with the electric calcined anthracite.Take by weighing cathode base thickener 1450Kg, weight-adding hammer and vibrate 45sec in the moulding box of the wide 560mm of long 3620mm is mentioned weight, with surface galling, evenly spreads compound material 80Kg with special tool, relays lower heavy punch and vibrates 2min butt mould, cooling.Come out of the stove after 230h adds thermal bake-out, process, check that composite bed and matrix closely combine together, no sharp interface, its thickness are 24mm, do not have cracking, no aliquation, through test can with the metal aluminium liquid complete wetting.
Embodiment 2
Other parameter is identical with example 1, wherein use 50L heating agent (or electrically heated) to mix and pinch pot, with heavy total ingredients by weight than being 70% titanium boride carbon composite, 13% the broken batching of graphite.Wherein titanium boride carbon composite mass ratio is: granularity is the titanium boride matrix material of 6-3mm: 16%; Granularity is a 0-3mm titanium boride carbon composite: 31%; Titanium boride powder: 40%; The broken 3-0mm 13% of graphite; Coal-tar pitch consumption 22% in the thickener.
In the moulding box of 3300 * 545mm, evenly tile earlier and mixed the matrix thickener 1320Kg that pinches, add composite bed thickener 29.5Kg then, cover on the matrix thickener, use the seaming chuck of novel texture, the demoulding behind the vibration 3min, obtaining green compact is 3300 * 545 * 470mm, the working face pitch angle is the cathode carbon pieces of 4 degree, adds, checks through cooling, roasting, machine.Composite bed and matrix form one, no sharp interface, working face is smooth, the about 10mm of composite bed thickness, through test can with the metal aluminium liquid complete wetting.
Claims (4)
1. the preparation method of a wetable cathode carbon piece comprises batching, cathode base vibratory compaction, compound coating layer vibratory compaction and sintering process on cathode base; The titanium boride that adds when it is characterized in that the batching of compound coating layer on cathode base in the preparation process be mix with granular warp pinch, titanium boride carbon composite form that moulding, sintering form adds.
2. the preparation method of a kind of wetable cathode carbon piece according to claim 1, the titanium boride weight content that it is characterized in that its particulate state titanium boride carbon composite is 80%.
3. the preparation method of a kind of wetable cathode carbon piece according to claim 1, the production that it is characterized in that the titanium boride carbon composite is to be siccative with synthetic graphite material, titanium boride powder, make binding agent with coal-tar pitch, use the production method of common carbon material, pinch by mixing, moulding, roasting process make.
4. the preparation method of a kind of wetable cathode carbon piece according to claim 1, it is characterized in that the titanium boride part in its titanium boride carbon composite layer thickener adds with titanium boride carbon composite particle form, part adds with the titanium boride powder form, and its siccative weight consists of: granularity is the titanium boride matrix material of 6-3mm: 16%-30%; Granularity is 3-0mm titanium boride carbon composite: 10%-20%; Granularity is the broken 10%-15% of 3-0mm graphite, titanium boride powder: 10%-40%; Coal-tar pitch in the thickener is 18%-23%.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610140573XA CN100491600C (en) | 2006-10-18 | 2006-10-18 | Method for preparing carbon block of cathode capable of being humidified |
| PCT/CN2006/003315 WO2008046255A1 (en) | 2006-10-18 | 2006-12-06 | A method for producing wettable cathode carbon blocks |
| DE112006004078T DE112006004078B4 (en) | 2006-10-18 | 2006-12-06 | Process for the preparation of wettable cathode blocks |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610140573XA CN100491600C (en) | 2006-10-18 | 2006-10-18 | Method for preparing carbon block of cathode capable of being humidified |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1958857A CN1958857A (en) | 2007-05-09 |
| CN100491600C true CN100491600C (en) | 2009-05-27 |
Family
ID=38070706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610140573XA Active CN100491600C (en) | 2006-10-18 | 2006-10-18 | Method for preparing carbon block of cathode capable of being humidified |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100491600C (en) |
| DE (1) | DE112006004078B4 (en) |
| WO (1) | WO2008046255A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255568B (en) * | 2007-12-07 | 2010-11-10 | 中南大学 | Particle gradation functional gradient TiB2/C composite cathode for aluminium electrolysis and preparation method thereof |
| DE102010038669A1 (en) | 2010-07-29 | 2012-02-02 | Sgl Carbon Se | Cathode block for an aluminum electrolysis cell and a method for its production |
| DE102010038665A1 (en) | 2010-07-29 | 2012-02-02 | Sgl Carbon Se | A method of manufacturing a cathode block for an aluminum electrolytic cell and a cathode block |
| DE102010038650A1 (en) | 2010-07-29 | 2012-02-02 | Sgl Carbon Se | A method of making a cathode block for an aluminum electrolytic cell and a cathode block |
| CN102002731B (en) * | 2010-10-14 | 2013-08-14 | 王飚 | Energy-saving fused salt aluminum electrolysis cell and method thereof |
| DE102011004013A1 (en) * | 2011-02-11 | 2012-08-16 | Sgl Carbon Se | Graphitized cathode block with an abrasion resistant surface |
| DE102011004001A1 (en) * | 2011-02-11 | 2012-08-16 | Sgl Carbon Se | Hard material-containing surface profiled cathode block |
| DE102011004014A1 (en) * | 2011-02-11 | 2012-08-16 | Sgl Carbon Se | Cathode block with a covering layer containing hard material |
| DE102012201468A1 (en) | 2012-02-01 | 2013-08-01 | Sgl Carbon Se | A method of making a cathode block for an aluminum electrolytic cell and a cathode block |
| CN102689907A (en) * | 2012-05-30 | 2012-09-26 | 深圳市新星轻合金材料股份有限公司 | Preparing method and application of transition metal boride |
| CN105780054B (en) * | 2016-04-27 | 2018-04-20 | 新疆大学 | The aluminium electrolytic cell cathode of cathode is used as using aluminium |
| CN105780053B (en) * | 2016-04-27 | 2018-08-17 | 新疆大学 | A kind of aluminum electrolysis method using aluminium as cathode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180182B1 (en) * | 1995-08-07 | 2001-01-30 | Moltech Invent S.A. | Hard and abrasion resistant surfaces protecting cathode blocks of aluminium electrowinning |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4526669A (en) * | 1982-06-03 | 1985-07-02 | Great Lakes Carbon Corporation | Cathodic component for aluminum reduction cell |
| DE3715178C2 (en) * | 1987-05-07 | 1998-04-09 | Vaw Ver Aluminium Werke Ag | Process for the production of a refractory, iron and slag resistant oxide-carbon stone |
| FR2789093B1 (en) * | 1999-02-02 | 2001-03-09 | Carbone Savoie | GRAPHITE CATHODE FOR ALUMINUM ELECTROLYSIS |
-
2006
- 2006-10-18 CN CNB200610140573XA patent/CN100491600C/en active Active
- 2006-12-06 WO PCT/CN2006/003315 patent/WO2008046255A1/en active Application Filing
- 2006-12-06 DE DE112006004078T patent/DE112006004078B4/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6180182B1 (en) * | 1995-08-07 | 2001-01-30 | Moltech Invent S.A. | Hard and abrasion resistant surfaces protecting cathode blocks of aluminium electrowinning |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1958857A (en) | 2007-05-09 |
| DE112006004078T5 (en) | 2009-10-08 |
| WO2008046255A1 (en) | 2008-04-24 |
| DE112006004078B4 (en) | 2013-06-13 |
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