CN101876079A - Titanium boride cathode material for aluminium electrolysis and preparation method thereof - Google Patents
Titanium boride cathode material for aluminium electrolysis and preparation method thereof Download PDFInfo
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- CN101876079A CN101876079A CN 201010207080 CN201010207080A CN101876079A CN 101876079 A CN101876079 A CN 101876079A CN 201010207080 CN201010207080 CN 201010207080 CN 201010207080 A CN201010207080 A CN 201010207080A CN 101876079 A CN101876079 A CN 101876079A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000004411 aluminium Substances 0.000 title claims abstract description 43
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000010936 titanium Substances 0.000 title claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000005238 degreasing Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000004898 kneading Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 15
- 239000004917 carbon fiber Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000012745 toughening agent Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000005056 compaction Methods 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 229920003987 resole Polymers 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract description 8
- 229910033181 TiB2 Inorganic materials 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000000280 densification Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000007731 hot pressing Methods 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 2
- 239000012744 reinforcing agent Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 under 50 °C Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
The invention discloses a titanium boride cathode material for aluminium electrolysis and a preparation method thereof and relates to a formula of an inert wettable cathode material for the aluminium electrolysis and the preparation method of the material. The titanium boride cathode material for aluminium electrolysis and the preparation method thereof are characterized in that: the cathode material comprises titanium diboride (TiB2), graphite, a high-temperature binding agent M and a reinforcing agent X. The preparation process comprises the following steps of: (1) mixing materials, namely, mixing, kneading and stirring the TiB2, graphite powder C, the high-temperature binding agent M and the reinforcing agent X according to theoretical ingredient volume and drying the mixture; (2) forming and degreasing, namely, performing pressure forming on the mixed raw materials to obtain green bodies and degreasing the green bodies under inert atmosphere; and (3) sintering, namely, sintering the degreased green bodies under the protective inert atmosphere or vacuum. A TiB2-C composite material for the aluminium electrolysis cell has the advantages of high wettability with aluminium liquid, high conductivity and high wear resistance, the realization of the sintering densification of the material and the homogeneous forming of the TiB2-C cathode material under the condition of normal pressure and low temperature, and the manufacturing cost which is far lower than that of a hot-pressing process.
Description
Technical field
A kind of titanium boride cathode material for aluminium electrolysis and preparation method thereof relates to prescription of a kind of aluminum electrolysis inertia wettability cathode material and preparation method thereof.
Background technology
In the existing aluminium electrolytic industry, negative electrode not only will play the effect of conduction, also will bear the physical erosion and the chemical corrosion of high-temperature molten salt, so the quality of cathode material quality directly has influence on the work-ing life of electrolyzer.General common charcoal piece, semi-graphite or the greying goods of adopting of the negative electrode of existing aluminium cell, but its main drawback is bad to the wettability of aluminium liquid, be subject to the especially erosion of sodium salt of electrolyte melt, impel carbon cathode volumetric expansion and cracking, cause the electrolyzer early damage, the precipitation that forms at bottom land is difficult for discharging simultaneously, the long-term furnace bottom crust that easily forms, cause the furnace bottom pressure drop to raise groove condition variation.
In recent years, TiB
2Since have high-melting-point, high rigidity, strong conductivity, oxidation-resistance strong, with aluminium liquid good wettability, good advantages such as the fused salt corrosion of anti-the fluoride salt are arranged, become the preferred material of wettability negative electrode.
Patent US4377463 has introduced a kind of TiB
2-graphite-asphalt high-temperature sintering technology, wherein dividing temperature section controlled atmosphere is the key of material densification.Patent US4439382, US4465581 and US45026669 have introduced TiO
2-refinery coke-binding agent-B
2O
3/ H
3BO
3The high temperature sintering technology of system.Wherein patent US45026669 also relates to a kind of TiB
2" mushroom " structure of-C matrix material.Patent US4812280, US4929328, US6534428 and US4859124 have introduced TiB
2The hot pressing and sintering technique of material.Wherein add reactive metal Fe, Ni, Co or Si
3N
4, adopt heat pressing process can significantly reduce TiB
2The sintering temperature of densification.Patent US5543370 and US4275026 have introduced TiB
2-B
4The pressureless sintering densification technology of C/SiC matrix material.Patent CN101158047A and CN101158048A have introduced a kind of by vibratory compaction, directly the production method of the greying wettability cathode carbon pieces of synthetic titanium diboride layer.Patent CN1203216C, CN1245538C and CN1245537C have introduced a kind of preparation method of electrolysis of aluminum titanium boride cathode material with gradient function coating.
By above patent as can be known, at present, the wettable negative electrode of using in Aluminium Electrolysis is mainly by coating paint-on technique, TiB
2Vibratory compaction of-C particle and heat pressing process obtain.The TiB that adopts the coating paint-on technique to obtain
2-C negative electrode often needs electric heating device for baking dreg solidified coating, and with brush or fur Cylinder coating brush TiB
2Coating is to TiB
2The coating applied pressure is limited, causes TiB
2Coating is not ideal enough to the wettability of aluminium electrolytic cell cathode charcoal liner, does not reach moistening effect fully, thereby makes TiB
2Coating and carbon anode/cathode bonding are insecure.The TiB that adopts the vibratory compaction technology to obtain
2-C surface recombination negative electrode is a heterogeneous material, only can realize TiB
2The mechanical bond of functional layer and carbon basal body layer, and TiB
2The cohesive strength of layer and corrosion-resistant, abrasion resistance properties, there are in various degree problem and because such vibratory compaction TiB with the wettability of aluminium liquid etc.
2-C composite cathode is a heterogeneous material, and negative electrode only has one side to be rich TiB
2Layer can't satisfy the needs of aluminum electrolysis process.And the TiB that adopts heat pressing process to prepare
2Though/C composite cathode material can satisfy the technical requirements of efficient green novel aluminum electrolysis process substantially; but because its making and tooling cost are especially expensive; and there is obvious defects in this technology at aspects such as realizing material maximization, abnormally-structured design, can't accomplish scale production.
Summary of the invention
The deficiency that purpose of the present invention just exists at above-mentioned prior art, provide a kind of can be wetting with aluminium liquid height, refractory melts ionogen and oozes erosion and the erosion of aluminium liquid, high conduction and titanium boride cathode material for aluminium electrolysis and preparation method thereof cheaply.
A kind of titanium boride cathode material for aluminium electrolysis is characterized in that the composition of cathode material comprises TiB
2, graphite, high-temperature agglomerant M, toughener X.
A kind of titanium boride cathode material for aluminium electrolysis of the present invention is characterized in that the weight composition of described titanium boride cathode material comprises: graphite 10%～30%; High-temperature agglomerant M 5%-20%; Toughener X 0-2%; Surplus is TiB2 and unavoidable impurities.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention is characterized in that its preparation process may further comprise the steps:
(1) batch mixing: press theoretical dosage with TiB
2, graphite C powder, high temperature adhesive M, toughener X mix and pinch stirring, oven dry is handled;
(2) moulding, degreasing: mixing raw material is carried out pressure forming get green compact, and skimming treatment under inert atmosphere;
(3) sintering: degreasing blank is carried out sintering under protectiveness inert atmosphere or vacuum.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention, it is characterized in that in described batch mixing process, adding dispersion agent, dispersion agent is at least a in alcohol, acetone, the polyacrylamide solution, and addition is 0.1%～3.0% of a compound gross weight.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention is characterized in that the TiB in described batch mixing process
2Purity is 98%, and median size is about 5 μ m～10 μ m.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention is characterized in that graphite in described batch mixing process is at least a in natural graphite, the synthetic graphite, and purity is 99%, and median size is 1 μ m～100 μ m.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention, it is characterized in that high temperature bond phase M in described batch mixing process is at least a in modified pitch, refinery coke, Resins, epoxy, furane resin, the resol, wherein the weight content of modified pitch is for (with the cathode material total mass is radix, down together) 5%～20%, softening temperature is 100 ℃～150 ℃; The weight content of refinery coke is 0～5%; The Resins, epoxy model is E-44, and weight percentage is 0～5%; The weight percentage of resol is 0～5%; The weight percentage of furane resin is 0～5%.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention, it is characterized in that toughener in described batch mixing process is at least a among carbon fiber, carbon fiber powder, the TiC, wherein the carbon fiber weight percentage is for (with the cathode material total mass is radix, down together) 0～2%, median size is 1～2mm; The carbon fiber powder weight percentage is 0～2%, and average particle size range is 50～150 μ m; The TiC weight percent is 0～6%, and average particle size range is 1～5mm.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention is characterized in that at the described kneading temperature of pinching whipping process that mixes be 55～150 ℃, and mixing the time of pinching is 2～4h, and the oven dry processing of batch mixing process is carried out under 60～120 ℃.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention is characterized in that its pressure forming obtains TiB
2The process of-C matrix material green compact adopts mold pressing or cast-isostatic cool pressing method or vibratory compaction, and pressure is 80MPa～200MPa, and the forming mould temperature is 25～150 ℃.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention is characterized in that its skimming treatment temperature is 800 ℃～1000 ℃; The inert atmosphere that adopts in the skimming treatment process is at least a from Ar, CO
2, H
2Or their combination, degreasing time is 40h～100h, the atmosphere Control for Oxygen Content is at 10～50ppm.
The preparation method of a kind of titanium boride cathode material for aluminium electrolysis of the present invention, the atmosphere that it is characterized in that its sintering process are at least a from vacuum, Ar, CO
2, H
2Or their combination; Sintering time is 24h～72h, O in the sintering atmosphere
2Content is controlled to be 1ppm～10ppm, and sintering temperature is 1200 ℃～1800 ℃, and wherein preferred temperature is 1400 ℃～1750 ℃; Sintering process adopts the carbon dust landfill to carry out.
A kind of aluminum electrolyzing cell used TiB of the present invention
2-C matrix material, functional with aluminum-liquid wetting, the electric conductivity height, wear-resistant; Under atmospheric low-temperature, can realize the densification sintering of material, can realize TiB
2The homogeneous moulding of-C cathode material, manufacturing cost is far below heat pressing process.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
A kind of titanium boride cathode material for aluminium electrolysis, the composition of cathode material comprise TiB2, graphite, high-temperature agglomerant M, toughener X; Its weight consists of graphite 10%～30%; High-temperature agglomerant M 5%-20%; Toughener X 0-2%; Surplus is TiB2 and unavoidable impurities.Its preparation process may further comprise the steps:
(1) batch mixing: with TiB2, graphite C powder, high temperature adhesive M, toughener X, mix and pinch stirring, oven dry is handled;
(2) moulding, degreasing: mixing raw material is carried out pressure forming get green compact, and skimming treatment under inert atmosphere;
(3) sintering: degreasing blank is carried out sintering under protectiveness inert atmosphere or vacuum.
Embodiment 1
With the 60wt.% median size is the technical pure TiB of 1 μ m
2Powder, 6wt.% median size are that the TiC particle of 1～2mm, graphous graphite powder, the modifying asphalt of 5wt.%, 2wt.%E-44 Resins, epoxy, 2wt.% median size that the 20wt.% median size is 1 μ m are that carbon fiber powder, the 5wt.% furane resin of 50 μ m place to mix and pinch in the pot, in containing the medium-acetone of 3wt.%, mix to pinch and stir 2h in 55 ℃, dry 24h under 60 ℃ adopts bidirectional pressed moulding to obtain TiB under 100MPa pressure then
2-C matrix material green compact place electric furnace with green compact, adopt the mode (Ar) in the inertia protective atmosphere of carbon dust landfill to carry out degreasing, and skimming temp is 1000 ℃, and degreasing time is 100h, and oxygen level is 50ppm in the atmosphere; Rise to 1400 ℃ with the temperature rise rate of 50 ℃/h then under the protection of high-purity Ar and carry out sintering, soaking time is 4h, and oxygen level is 10ppm in the sintering atmosphere, and obtaining volume density is 2.30g/cm
3Sample.
Embodiment 2
With the 55wt.% median size is the technical pure TiB of 1 μ m
2Powder, 5wt.% median size are the technical pure TiB of 10mm
2Carbon fiber powder, 5wt.% furane resin, 2.2wt.% resol that particle, 10wt.% median size are the modifying asphalt of natural flake graphite powder, the 20wt.% of 100 μ m, carbon fiber that the 2wt.% median size is 1～2mm, the 0.8wt.% median size is 150 μ m place to mix to be pinched in the pot, in containing 3.5wt.% alcohol medium, under 60 ℃, mix to pinch and stir 4h, dry 24h under 80 ℃ adopts vibratory compaction to obtain TiB under 80MPa then
2-C matrix material green compact place electric furnace with green compact, adopt the mode (Ar) in the inertia protective atmosphere of carbon dust landfill to carry out degreasing, and skimming temp is 800 ℃, and degreasing time is 40h, and oxygen level is 10ppm in the atmosphere; Rise to 1200 ℃ with the temperature rise rate of 50 ℃/h then under the protection of high-purity Ar and carry out sintering, soaking time is 4h, and oxygen level is 1ppm in the sintering atmosphere, and obtaining volume density is 2.10g/cm
3Sample.
Embodiment 3
With the 70wt.% median size is the technical pure TiB of 1 μ m
2Powder, 5wt.% median size are the technical pure TiB of 5mm
2Particle, 2wt.% median size are that TiC particle, the 6.4wt.% median size of 1～2mm is that natural flake graphite powder, 5wt.% modifying asphalt, 10wt.% refinery coke, the 1.6wt.% median size of 10 μ m is that the carbon fiber powder of 50 μ m places to mix and pinches in the pot, in containing the 3wt.% medium-acetone, under 50 ℃, mix and pinch 2h, to mix then and pinch pot and be warming up to 150 ℃ and mix and to pinch 2h, mix to pinch material is placed in the loft drier at 80 times dry 24h after finishing, under 200MPa pressure, adopt vibratory compaction to get TiB
2-C matrix material green compact place electric furnace with green compact, adopt the mode (Ar) in the inertia protective atmosphere of carbon dust landfill to carry out degreasing, and skimming temp is 1000 ℃, and degreasing time is 80h, and oxygen level is 10ppm in the atmosphere; Rise to 1800 ℃ with the temperature rise rate of 100 ℃/h then under the protection of high-purity Ar and carry out sintering, soaking time is 4h, and oxygen level is 1ppm in the sintering atmosphere, and obtaining volume density is 2.65g/cm
3Sample.
Embodiment 4
With the 65wt% median size is the technical pure TiB of 1 μ m
2Powder, 6wt.% median size are that TiC particle, 7.5 median sizes of 1～2mm are that the resol of modifying asphalt, the 1wt.% of natural flake graphite powder, the 20wt.% of 10 μ m, carbon fiber powder that the 1.6wt.% median size is 50 μ m place to mix and pinch in the pot, in containing the 5wt.% polyacrylamide solution, under 55 ℃, mix and pinch 24h, then at 120 ℃ of following dry 2h, under 80MPa pressure, adopt vibratory compaction to obtain TiB after forming mould is heated to 150 ℃
2-C matrix material green compact place electric furnace with green compact, adopt the mode (Ar) in the inertia protective atmosphere of carbon dust landfill to carry out degreasing, and skimming temp is 1000 ℃, and degreasing time is 80h, and oxygen level is 10ppm in the atmosphere; Rise to 1750 ℃ with the temperature rise rate of 100 ℃/h then under the protection of high-purity Ar and carry out sintering, soaking time is 4h, and oxygen level is 1ppm in the sintering atmosphere, and obtaining volume density is 2.70g/cm
3Sample.
Claims (12)
1. a titanium boride cathode material for aluminium electrolysis is characterized in that the composition of cathode material comprises TiB
2, graphite, high-temperature agglomerant M, toughener X.
2. a kind of titanium boride cathode material for aluminium electrolysis according to claim 1 is characterized in that the weight composition of described titanium boride cathode material comprises: graphite 10%～30%; High-temperature agglomerant M 5%-20%; Toughener X 0-2%; Surplus is TiB
2And unavoidable impurities.
3. the preparation method of a titanium boride cathode material for aluminium electrolysis is characterized in that its preparation process may further comprise the steps:
(1) batch mixing: press theoretical dosage with TiB
2, graphite C powder, high temperature adhesive M, toughener X mix and pinch stirring, oven dry is handled;
(2) moulding, degreasing: mixing raw material is carried out pressure forming get green compact, and skimming treatment under inert atmosphere;
(3) sintering: degreasing blank is carried out sintering under protectiveness inert atmosphere or vacuum.
4. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3, it is characterized in that in described batch mixing process, adding dispersion agent, dispersion agent is at least a in alcohol, acetone, the polyacrylamide solution, and addition is 0.1%～3.0% of a compound gross weight.
5. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3 is characterized in that the TiB in described batch mixing process
2Purity is 98%, and median size is 1 μ m～10 μ m.
6. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3, it is characterized in that graphite in described batch mixing process is at least a in natural graphite, the synthetic graphite, purity is 99%, and median size is 1 μ m～100 μ m.
7. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3, it is characterized in that high temperature bond phase M in described batch mixing process is at least a in modified pitch, refinery coke, Resins, epoxy, furane resin, the resol, wherein the weight content of modified pitch is for being radix with the cathode material total mass, 5%～20%, softening temperature is 100 ℃～150 ℃; The weight content of refinery coke is 0～5%; The Resins, epoxy model is E-44, and weight percentage is 0～5%; The weight percentage of resol is 0～5%; The weight percentage of furane resin is 0～5%.
8. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3, it is characterized in that toughener in described batch mixing process is at least a among carbon fiber, carbon fiber powder, the TiC, wherein the carbon fiber weight percentage is for being radix with the cathode material total mass, 0～2%, median size is that 1～2mm carbon fiber powder weight percentage is 0～2%, and average particle size range is 50～150 μ m; The TiC weight percent is 0～6%, and average particle size range is 1～5mm.
9. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3, it is characterized in that at the described kneading temperature of pinching whipping process that mixes be 55～150 ℃, mixing the time of pinching is 2～4h, and the oven dry processing of batch mixing process is carried out under 60～120 ℃.
10. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3 is characterized in that its pressure forming obtains TiB
2The process of-C matrix material green compact adopts mold pressing or cast-isostatic cool pressing method or vibratory compaction, and pressure is 80MPa～200MPa, and the forming mould temperature is 25～150 ℃.
11. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 3 is characterized in that its skimming treatment temperature is 800 ℃～1000 ℃; The inert atmosphere that adopts in the skimming treatment process is at least a from Ar, CO
2, H
2Or their combination, degreasing time is 40h～100h, the atmosphere Control for Oxygen Content is at 10～50ppm.
12. the preparation method of a kind of titanium boride cathode material for aluminium electrolysis according to claim 4, the atmosphere that it is characterized in that its sintering process are at least a from vacuum, Ar, CO
2, H
2Or their combination; Sintering time is 24h～72h, O in the sintering atmosphere
2Content is controlled to be 1ppm～10ppm, and sintering temperature is 1200 ℃～1800 ℃, and wherein preferred temperature is 1400 ℃～1750 ℃; Sintering process adopts the carbon dust landfill to carry out.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212845A (en) * | 2011-05-24 | 2011-10-12 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| CN102304725A (en) * | 2011-09-16 | 2012-01-04 | 云南云铝润鑫铝业有限公司 | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof |
| CN102491753A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | TiB2 composite cathode material for aluminum electrolysis and preparation method thereof |
| CN102531657A (en) * | 2012-01-05 | 2012-07-04 | 武汉理工大学 | Method for preparing TiB2-Csf-Carbon composite material |
| CN103194101A (en) * | 2013-03-27 | 2013-07-10 | 江苏联合金陶特种材料科技有限公司 | Titanium boride-based coating composite material for aluminum electrolysis, preparation method and coating method thereof |
| CN109943865A (en) * | 2019-04-28 | 2019-06-28 | 镇江慧诚新材料科技有限公司 | A kind of oxygen aluminium coproduction cathode for electrolyzing material and preparation method thereof |
| CN110436933A (en) * | 2019-08-26 | 2019-11-12 | 中南大学 | A kind of TiB used for aluminium electrolysis2Graphene composite cathode material and preparation method thereof |
| CN113172224A (en) * | 2021-04-27 | 2021-07-27 | 浙江大学 | Preparation method of titanium-based composite structure material |
| CN115961310A (en) * | 2023-01-31 | 2023-04-14 | 中铝郑州有色金属研究院有限公司 | Titanium diboride wettable cathode |
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| CN1552948A (en) * | 2003-05-28 | 2004-12-08 | 中南大学 | Preparation of composite titanium boride cathode for guide aluminium eledrolyzing tank |
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Cited By (16)
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|---|---|---|---|---|
| CN102212845A (en) * | 2011-05-24 | 2011-10-12 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| CN102212845B (en) * | 2011-05-24 | 2012-10-31 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| CN102304725A (en) * | 2011-09-16 | 2012-01-04 | 云南云铝润鑫铝业有限公司 | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof |
| CN102491753A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | TiB2 composite cathode material for aluminum electrolysis and preparation method thereof |
| CN102531657A (en) * | 2012-01-05 | 2012-07-04 | 武汉理工大学 | Method for preparing TiB2-Csf-Carbon composite material |
| CN102531657B (en) * | 2012-01-05 | 2013-11-20 | 武汉理工大学 | Method for preparing TiB2-Csf-Carbon composite material |
| CN103194101A (en) * | 2013-03-27 | 2013-07-10 | 江苏联合金陶特种材料科技有限公司 | Titanium boride-based coating composite material for aluminum electrolysis, preparation method and coating method thereof |
| CN103194101B (en) * | 2013-03-27 | 2016-03-09 | 江苏联合金陶特种材料科技有限公司 | A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method |
| CN109943865A (en) * | 2019-04-28 | 2019-06-28 | 镇江慧诚新材料科技有限公司 | A kind of oxygen aluminium coproduction cathode for electrolyzing material and preparation method thereof |
| CN110436933A (en) * | 2019-08-26 | 2019-11-12 | 中南大学 | A kind of TiB used for aluminium electrolysis2Graphene composite cathode material and preparation method thereof |
| CN110436933B (en) * | 2019-08-26 | 2021-11-05 | 中南大学 | TiB for aluminum electrolysis2-graphene composite cathode material and preparation method thereof |
| CN113172224A (en) * | 2021-04-27 | 2021-07-27 | 浙江大学 | Preparation method of titanium-based composite structure material |
| CN113172224B (en) * | 2021-04-27 | 2022-03-01 | 浙江大学 | Preparation method of titanium-based composite structure material |
| CN115961310A (en) * | 2023-01-31 | 2023-04-14 | 中铝郑州有色金属研究院有限公司 | Titanium diboride wettable cathode |
| CN115961310B (en) * | 2023-01-31 | 2023-12-12 | 中铝郑州有色金属研究院有限公司 | Titanium diboride wettable cathode |
| WO2024159636A1 (en) * | 2023-01-31 | 2024-08-08 | 中铝郑州有色金属研究院有限公司 | Titanium diboride wettable cathode |
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