CN101643922B - Method for producing aluminum alloy and special pre-baking carbon anode block thereof - Google Patents
Method for producing aluminum alloy and special pre-baking carbon anode block thereof Download PDFInfo
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- CN101643922B CN101643922B CN2009103068471A CN200910306847A CN101643922B CN 101643922 B CN101643922 B CN 101643922B CN 2009103068471 A CN2009103068471 A CN 2009103068471A CN 200910306847 A CN200910306847 A CN 200910306847A CN 101643922 B CN101643922 B CN 101643922B
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title abstract description 18
- 239000002006 petroleum coke Substances 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 29
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 29
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 sodium aluminum fluoride Chemical compound 0.000 claims description 62
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 44
- 239000011294 coal tar pitch Substances 0.000 claims description 32
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 30
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 22
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 229910000737 Duralumin Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 22
- 239000010936 titanium Substances 0.000 abstract description 19
- 229910052719 titanium Inorganic materials 0.000 abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052706 scandium Inorganic materials 0.000 abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 12
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 239000011280 coal tar Substances 0.000 abstract 1
- 229910001610 cryolite Inorganic materials 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 30
- 239000002562 thickening agent Substances 0.000 description 30
- 229910052782 aluminium Inorganic materials 0.000 description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 20
- 239000004411 aluminium Substances 0.000 description 17
- 229910000542 Sc alloy Inorganic materials 0.000 description 15
- 229910001093 Zr alloy Inorganic materials 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 238000000748 compression moulding Methods 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000011800 void material Substances 0.000 description 10
- 229910001069 Ti alloy Inorganic materials 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
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- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for producing aluminum alloy and special pre-baking carbon anode block thereof. The special pre-baking carbon anode block of the invention is prepared by at least two of the forged petroleum coke, coal tar and the oxides as follows: zirconium dioxide, discandium trioxide and titanium dioxide; the pre-baking carbon anode block is roasted to obtain the pre-baking carbon anode; the roasting temperature is 1150-1250 DEG C and the time is 600-720 h. The method for producing aluminum alloy of the invention takes the pre-baking carbon anode as the anode and produces the aluminum alloy through electrolyzing the aluminum oxide in the electrolyte of cryolite. The physical and chemical indexes of the pre-baking carbon anode have no change basically. The titanium, scandium and zirconium are added uniformly into the aluminum alloy by using the anode to produce the aluminum alloy, and the yield of metal is high.
Description
Technical field
The present invention relates to produce the method and the special pre-baking carbon anode block of duraluminum.
Background technology
Technical pure is electrolytic production of aluminum generally to be under 920～～970 ℃, with sodium aluminum fluoride (Na
3AlF
6) be solvent, add multiple additives such as AlF
3, MgF
2, CaF
2Deng electrolyte system, realize through dissolving and electrolytic oxidation aluminium powder.If can utilize the electrolyzer of fine aluminium; Under the prerequisite that not increase equipment drops into basically, adopt the electrolysis process and the parameter of fine aluminium, through in aluminium cell, adding some MOX; And do not influence under the prerequisite of main electrolysis index; Directly the aluminium base master alloy of electrolysis production will reduce energy consumption, reduces its cost by a relatively large margin.Produce aluminium intermediate alloy in the industry, extensively adopt the method that directly in molten aluminum, adds alloying element to produce, this method is prone to cause the free loss of metal and higher energy expenditure.
In general, the Gibbs free energy that the fused salt electrolysis duraluminum satisfies thermite reduction reaction is a negative value, deposition potential less than or approach the aluminium deposition potential and all can carry out electrolysis and produce duraluminum.Electrolytic process produces metal and master alloy has the purity height, produces aluminum base alloy flow process weak point, and cost and comprehensive energy consumption are lower, and alloy property is more superior than mix-melting method, so be used widely.Ti is very effective grain-refining agent in duraluminum, when adding little amount of titanium in the aluminum base alloy, and Al
3The nucleating center of Ti phase makes a～Al aluminum alloy organization can obtain obvious refinement, and intensity, toughness, wear resistance, anti-fatigue performance and the thermostability etc. of alloy all increase simultaneously.Contain in the scandium-aluminium alloy if join titanium, not only strengthened its thinning effect, the more important thing is that Ti can replace Al
3Sc in the Sc particle generates Al
3(Sc
xTi
1～x) composite particles, and do not change original Al
3The excellent properties of Sc particle, Sc, Ti can increase significantly to the performance of alloy after uniting interpolation.Zr can make Al
3The Sc facies evolution forms Al
3(Sc, Zr) composite particles have extremely strong grain refining effect.Zr is the crystal grain of refinement alloy consumingly, can significantly improve the recrystallization temperature of alloy, and strongly inhibited improves intensity, plasticity and the fracture toughness property of alloy along brilliant fracture tendency.
Summary of the invention
The purpose of this invention is to provide a kind of method and special pre-baking carbon anode block of producing duraluminum, purpose is the problem that solves the lack of homogeneity of metal scandium, titanium, zirconium in the duraluminum.
Special pre-baking carbon anode block provided by the present invention, by in after-smithing petroleum coke, coal-tar pitch and the following oxide compound at least two kinds process: ZIRCONIUM DIOXIDE 99.5, scandium oxide and titanium oxide.
Wherein, by weight percentage, said after-smithing petroleum coke is 70～82%; Said coal-tar pitch is 15～28%; Said scandium oxide is 0～6%; Said ZIRCONIUM DIOXIDE 99.5 is 0～5%; Said titanium oxide is 0～5%.
Described pre-baking carbon anode block can be confirmed the amount of titanium oxide, scandium oxide and ZIRCONIUM DIOXIDE 99.5 in the said pre-baking carbon anode block according to the content of titanium, scandium and zirconium in the alloy.If produce aluminium zirconium scandium alloy, just need not to add titanium oxide, this moment, said pre-baking carbon anode block can be processed by 72～81% said after-smithing petroleum cokes, 17% said coal-tar pitch, 1～6% said scandium oxide and 1～5% said ZIRCONIUM DIOXIDE 99.5.If produce aluminium titanium scandium alloy; Only need to add scandium oxide and titanium oxide, said pre-baking carbon anode block can be processed by 74～81% said after-smithing petroleum cokes, 15～17% said coal-tar pitch, 1～6% said scandium oxide and 1～5% said titanium oxide.If produce the aluminium titanium-zirconium alloy, need not to add scandium oxide, said pre-baking carbon anode block can be processed by 75～81% said after-smithing petroleum cokes, said coal-tar pitch 15～17%, 1～5% said titanium oxide and 1～5% said ZIRCONIUM DIOXIDE 99.5.Want to produce aluminium titanium zirconium scandium alloy, said pre-baking carbon anode block will contain scandium oxide, titanium oxide and ZIRCONIUM DIOXIDE 99.5, described pre-baking carbon anode block can be processed by 70～82% said after-smithing petroleum cokes, 15～28% said coal-tar pitch, 0.5～5% said scandium oxide, 1～5% said titanium oxide and 0.5～5% said ZIRCONIUM DIOXIDE 99.5.
Described after-smithing petroleum coke and pitch can be the after-smithing petroleum coke and the pitch of all size.
The after-smithing petroleum coke quality standard specifically can be:
Resistivity :≤550 Ω mm
2/ m;
True density: 2.0～2.08g/cm
3
Moisture content :≤0.3%.
The asphalt quality standard specifically can be:
Softening temperature: 75～95 ℃ of middle temperature, 95～120 ℃ of high temperature;
Toluene is not tolerant :≤25%;
Quinoline is not tolerant :≤10%;
Ash content :≤0.5%;
Moisture content :≤5.0;
Fugitive constituent: 55～75%.
Described pre-baking carbon anode block can obtain pre-baked carbon anode through after the roasting; The temperature of said roasting is 1150～1250 ℃, and the time is 600～720 hours.
The method of production duraluminum provided by the present invention is to be anode with described pre-baked carbon anode, electrolysis of aluminum oxide for producing aluminum alloy in containing the ionogen of sodium aluminum fluoride.
Wherein, also can contain mass percentage concentration 4～5% Calcium Fluoride (Fluorspan), mass percentage concentration 2～3% Sellaites and mass percentage concentration 1.5～2% lithium fluoride in the said ionogen.
Said sodium aluminum fluoride molecular ratio is 2.2～2.6.
The mass percent concentration of said aluminum oxide can be 1.5～3.5%, certainly also comprises the scope that alumina concentration 1.9～3.5% is such.
In the method for said electrolysis production duraluminum, electrolysis temperature can be 920～980 ℃; Bath voltage is 3.8～4.5V; Pole span is 3.0～5.0 centimetres, also comprises 4.0～4.9 centimetres.
The basic no change of the physical and chemical index of pre-baked carbon anode of the present invention.With this anode production duraluminum, titanium, scandium and zirconium add evenly in the duraluminum, and the metal yield is high.The present invention need not to use pure metal, thereby can reduce the cost of producing aluminium titanium scandium zirconium alloy significantly, helps applying of aluminium titanium scandium zirconium alloy.
Embodiment
The after-smithing petroleum coke quality standard is among the following embodiment:
Resistivity :≤550 Ω mm
2/ m;
True density: 2.0～2.08g/cm
3
Moisture content :≤0.3%.
The asphalt quality standard is:
Softening temperature: 75～95 ℃ of middle temperature, 95～120 ℃ of high temperature;
Toluene is not tolerant :≤25%;
Quinoline is not tolerant :≤10%;
Ash content :≤0.5%;
Moisture content :≤5.0;
Fugitive constituent: 55～75%.
Embodiment 1, production aluminium zirconium scandium alloy
After-smithing petroleum coke, coal-tar pitch, scandium oxide and ZIRCONIUM DIOXIDE 99.5 are mixed; Be placed on to mix to pinch in the pot and be made as thickener in 50 minutes 100 ℃ of mixed down pinching; By weight percentage, after-smithing petroleum coke accounts for 81% in the thickener, and coal-tar pitch accounts for 17%, scandium oxide accounts for 1%, ZIRCONIUM DIOXIDE 99.5 accounts for 1%; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1150 ℃, and the time is to prepare pre-baked carbon anode in 720 hours.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 1.
The physical and chemical index of the pre-baked carbon anode of table 1. embodiment 1
| Ash % | 0.5 | Resistivity Ω mm 2/m | 55 |
| Compressive strength MPa | 32 | Volume density g/cm 3 | 1.56 |
| Void content % | ＜26 | True density g/cm 3 | 2.06 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 4%, the mass percent concentration of Sellaite is 2%, the mass percent concentration of lithium fluoride is 1.5%, the molecular ratio 2.35 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 2.5%.920 ℃ of electrolysis temperatures; Bath voltage 4.125V; 4.3 centimetres of pole spans.
After 120 hours, obtain aluminium zirconium scandium alloy, the weight percent of aluminium zirconium scandium alloy consists of: scandium 0.23%, zirconium 0.29%, all the other be aluminium and unavoidable impurities, Fe in the impurity＜0.15%, Si＜0.12%, and other impurity is micro-.
Embodiment 2, production aluminium titanium-zirconium alloy
After-smithing petroleum coke, coal-tar pitch, titanium oxide and ZIRCONIUM DIOXIDE 99.5 are mixed; Be placed on to mix to pinch in the pot and be made as thickener in 20 minutes 200 ℃ of mixed down pinching; By weight percentage for after-smithing petroleum coke accounts for 81%, coal-tar pitch accounts for 17%, titanium oxide accounts for 1%, ZIRCONIUM DIOXIDE 99.5 accounts for 1% in the thickener; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block; Pre-baking carbon anode block is placed the roasting kiln roasting, and the temperature of roasting is 1250 ℃, and the time is 600 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 2.
The physical and chemical index of the pre-baked carbon anode of table 2. embodiment 2
| Ash % | 0.5 | Resistivity Ω mm 2/m | 56 |
| Compressive strength MPa | 31 | Volume density g/cm 3 | 1.55 |
| Void content % | ＜26 | True density g/cm 3 | 2.04 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 5%, the mass percent concentration of Sellaite is 3%, the mass percent concentration of lithium fluoride is 2%, the molecular ratio 2.50 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 3.5%.960 ℃ of electrolysis temperatures; Bath voltage 4.5V; 4.9 centimetres of pole spans.
After 150 hours, obtain the aluminium titanium-zirconium alloy, the weight percent of aluminium titanium-zirconium alloy consists of: titanium 0.22%, zirconium 0.29%, all the other be aluminium and unavoidable impurities, Fe in the impurity＜0.15%, Si＜0.12%, and other impurity is micro-.
Embodiment 3, production aluminium titanium scandium alloy
With after-smithing petroleum coke, coal-tar pitch, scandium oxide and titanium oxide mix, and are placed on to mix to pinch in the pot to be made as thickener in 50 minutes 200 ℃ of mixed down pinching; By weight percentage, after-smithing petroleum coke accounts for 81% in the thickener, and coal-tar pitch accounts for 17%, scandium oxide accounts for 1%, titanium oxide accounts for 1%; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1150 ℃, and the time is 720 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 3.
The physical and chemical index of the pre-baked carbon anode of table 3. embodiment 3
| Ash % | 0.6 | Resistivity Ω mm 2/m | 57 |
| Compressive strength MPa | 30 | Volume density g/cm 3 | 1.54 |
| Void content % | ＜26 | True density g/cm 3 | 2.03 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 4%, the mass percent concentration of Sellaite is 2%, the mass percent concentration of lithium fluoride is 1.5%, the molecular ratio 2.40 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 2.0%.950 ℃ of electrolysis temperatures; Bath voltage 4.1V; 4.0 centimetres of pole spans.
After 150 hours, obtain aluminium titanium scandium alloy, the weight percent of aluminium titanium scandium alloy consists of: scandium 0.295%, titanium 0.23%, all the other be aluminium, and unavoidable impurities, Fe in the impurity＜0.15%, Si＜0.12%, and other impurity is micro-.
Embodiment 4, production aluminium titanium scandium zirconium alloy
After-smithing petroleum coke, coal-tar pitch, scandium oxide, titanium oxide and ZIRCONIUM DIOXIDE 99.5 mixing are placed on mixed pinching in the pot were made as thickener in 50 minutes 200 ℃ of mixed down pinching; By weight percentage, after-smithing petroleum coke accounts for 80%, coal-tar pitch accounts for 17%, scandium oxide accounts for 1%, titanium oxide accounts for 1%, ZIRCONIUM DIOXIDE 99.5 accounts for 1% in the thickener; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1250 ℃, and the time is 600 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 4.
The physical and chemical index of the pre-baked carbon anode of table 4. embodiment 4
| Ash % | 0.5 | Resistivity Ω mm 2/m | 56 |
| Compressive strength MPa | 30 | Volume density g/cm 3 | 1.55 |
| Void content % | ＜26 | True density g/cm 3 | 2.04 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 5%, the mass percent concentration of Sellaite is 3%, the mass percent concentration of lithium fluoride is 2%, the molecular ratio 2.50 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 3.5%.960 ℃ of electrolysis temperatures; Bath voltage 4.125V; 4.3 centimetres of pole spans.
After 120 hours; Obtain aluminium titanium scandium zirconium alloy; The weight percent of aluminium titanium scandium zirconium alloy consists of: scandium 0.289%, titanium 0.227%, zirconium 0.236%, all the other are aluminium and unavoidable impurities, Fe in the impurity＜0.15%, Si＜0.12%, other impurity trace.
Embodiment 5, production aluminium titanium scandium zirconium alloy
After-smithing petroleum coke, coal-tar pitch, scandium oxide, titanium oxide and ZIRCONIUM DIOXIDE 99.5 are mixed, be placed on mixed pinching in the pot and be made as thickener in 50 minutes 200 ℃ of mixed down pinching; In the thickener by weight percentage, with after-smithing petroleum coke account for 70%, coal-tar pitch accounts for 15%, scandium oxide accounts for 5%, titanium oxide account for 5% and ZIRCONIUM DIOXIDE 99.5 account for 5%; Thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1150 ℃, and the time is 720 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 5.
The physical and chemical index of the pre-baked carbon anode of table 5. embodiment 5
| Ash % | 0.8 | Resistivity Ω mm 2/m | 59 |
| Compressive strength MPa | 31 | Volume density g/cm 3 | 1.55 |
| Void content % | ＜26 | True density g/cm 3 | 2.06 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 5%, the mass percent concentration of Sellaite is 3%, the mass percent concentration of lithium fluoride is 1.5%, the molecular ratio 2.50 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 1.9%.960 ℃ of electrolysis temperatures; Bath voltage 4.125V; 4.3 centimetres of pole spans.
After 150 hours, obtain aluminium scandium titanium alloy, the weight percent of aluminium scandium titanium alloy consists of: scandium 0.585%, titanium 0.461%, zirconium 0.472%, all the other be aluminium and unavoidable impurities, Fe in the impurity＜0.15%, Si＜0.12%, and other impurity is micro-.
Embodiment 6, production aluminium titanium scandium zirconium alloy
After-smithing petroleum coke, coal-tar pitch, scandium oxide, titanium oxide and ZIRCONIUM DIOXIDE 99.5 are mixed, be placed on mixed pinching in the pot and be made as thickener in 20 minutes 200 ℃ of mixed down pinching; In the thickener by weight percentage; After-smithing petroleum coke accounts for 82%, coal-tar pitch accounts for 15%, scandium oxide accounts for 1%, titanium oxide accounts for 1%, ZIRCONIUM DIOXIDE 99.5 accounts for 1%, and thickener is added compression moulding in the shaper, obtains pre-baking carbon anode block; Pre-baking carbon anode block is placed the roasting kiln roasting; The temperature of roasting is 1250 ℃, and the time is 600 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 6.
The physical and chemical index of the pre-baked carbon anode of table 6. embodiment 6
| Ash % | 0.6 | Resistivity Ω mm 2/m | 56 |
| Compressive strength MPa | 29 | Volume density g/cm 3 | 1.55 |
| Void content % | ＜26 | True density g/cm 3 | 2.04 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 5%, the mass percent concentration of Sellaite is 2%, the mass percent concentration of lithium fluoride is 1.5%, the molecular ratio 2.40 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 3.1%.950 ℃ of electrolysis temperatures; Bath voltage 4.125V; 4.3 centimetres of pole spans.
After 150 hours, obtain aluminium scandium titanium alloy, the weight percent of aluminium scandium titanium alloy consists of: scandium 0.287%, titanium 0.225%, zirconium 0.235%, all the other be aluminium and unavoidable impurities, Fe in the impurity＜0.16%, Si＜0.13%, and other impurity is micro-.
Embodiment 7, production aluminium titanium scandium zirconium alloy
After-smithing petroleum coke, coal-tar pitch, scandium oxide, titanium oxide, ZIRCONIUM DIOXIDE 99.5 are mixed; Be placed on to mix to pinch in the pot and be made as thickener in 20 minutes 200 ℃ of mixed down pinching; By weight percentage, after-smithing petroleum coke accounts for 70%, coal-tar pitch accounts for 28%, scandium oxide accounts for 0.5%, titanium oxide accounts for 1%, ZIRCONIUM DIOXIDE 99.5 accounts for 0.5% in the thickener; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1250 ℃, and the time is 600 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 7.
The physical and chemical index of the pre-baked carbon anode of table 7. embodiment 7
| Ash % | 0.6 | Resistivity Ω mm 2/m | 56 |
| Compressive strength MPa | 29 | Volume density g/cm 3 | 1.55 |
| Void content % | ＜26 | True density g/cm 3 | 2.04 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 5%, the mass percent concentration of Sellaite is 3%, the mass percent concentration of lithium fluoride is 1.5%, the molecular ratio 2.45 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 2.6%.950 ℃ of electrolysis temperatures; Bath voltage 4.125V; 4.3 centimetres of pole spans.
After 150 hours, obtain aluminium scandium titanium alloy, the weight percent of aluminium scandium titanium alloy consists of: scandium 0.146%, titanium 0.114%, zirconium 0.119%, all the other be aluminium and unavoidable impurities, Fe in the impurity＜0.16%, Si＜0.13%, and other impurity is micro-.
Embodiment 8, production aluminium zirconium scandium alloy
With after-smithing petroleum coke; Coal-tar pitch, scandium oxide, ZIRCONIUM DIOXIDE 99.5 mix, be placed on to mix to pinch in the pot to mix to pinch down to be made as thickener in 50 minutes at 100 ℃, in the thickener by weight percentage; After-smithing petroleum coke accounts for 72%, and coal-tar pitch accounts for 17%, scandium oxide accounts for 6%, ZIRCONIUM DIOXIDE 99.5 accounts for 5%; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1250 ℃, and the time is 600 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 8.
The physical and chemical index of the pre-baked carbon anode of table 8. embodiment 8
| Ash % | 0.6 | Resistivity Ω mm 2/m | 56 |
| Compressive strength MPa | 29 | Volume density g/cm 3 | 1.55 |
| Void content % | ＜26 | True density g/cm 3 | 2.04 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 4%, the mass percent concentration of Sellaite is 2%, the mass percent concentration of lithium fluoride is 1.5%, the molecular ratio 2.35 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 2.5%.950 ℃ of electrolysis temperatures; Bath voltage 4.125V; 4.3 centimetres of pole spans.
After 150 hours, obtain aluminium zirconium scandium alloy, the weight percent of aluminium zirconium scandium alloy consists of: scandium 1.675%, zirconium 1.128%, all the other be aluminium and unavoidable impurities, Fe in the impurity＜0.15%, silicon Si＜0.12%, and other impurity is micro-.
Embodiment 9, production aluminium titanium-zirconium alloy
After-smithing petroleum coke, coal-tar pitch, titanium oxide and ZIRCONIUM DIOXIDE 99.5 are mixed; Be placed on to mix to pinch in the pot to mix to pinch down at 200 ℃ and be made as thickener in 20 minutes, after-smithing petroleum coke accounts for 75% by weight percentage in the thickener, coal-tar pitch accounts for 15%, titanium oxide accounts for 5%, ZIRCONIUM DIOXIDE 99.5 accounts for 5%; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1250 ℃, and the time is 600 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 9.
The physical and chemical index of the pre-baked carbon anode of table 9. embodiment 9
| Ash % | 0.6 | Resistivity Ω mm 2/m | 56 |
| Compressive strength MPa | 29 | Volume density g/cm 3 | 1.55 |
| Void content % | ＜26 | True density g/cm 3 | 2.04 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 5%, the mass percent concentration of Sellaite is 3%, the mass percent concentration of lithium fluoride is 5%, the molecular ratio 2.50 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 3.5%.960 ℃ of electrolysis temperatures; Bath voltage 4.5V; 4.8 centimetres of pole spans.
After 150 hours, obtain the aluminium titanium-zirconium alloy, the weight percent of aluminium titanium-zirconium alloy consists of: titanium 1.119%, zirconium 1.157%, all the other be aluminium and unavoidable impurities, Fe in the impurity＜0.15%, Si＜0.12%, and other impurity is micro-.
Embodiment 10, production aluminium titanium scandium alloy
After-smithing petroleum coke, coal-tar pitch, scandium oxide and titanium oxide are mixed, be placed on to mix to pinch in the pot to mix to pinch down at 200 ℃ and be made as thickener in 50 minutes, by weight percentage, after-smithing petroleum coke accounts for 74% in the thickener, and coal-tar pitch accounts for 15%, scandium oxide accounts for 6%; Titanium oxide accounts for 5%; Again thickener is added compression moulding in the shaper, obtain pre-baking carbon anode block, pre-baking carbon anode block is placed the roasting kiln roasting, the temperature of roasting is 1250 ℃, and the time is 600 hours, prepares pre-baked carbon anode.
The physical and chemical index of the pre-baked carbon anode that obtains is as shown in table 10.
The physical and chemical index of the pre-baked carbon anode of table 10. embodiment 10
| Ash % | 0.8 | Resistivity Ω mm 2/m | 59 |
| Compressive strength MPa | 32 | Volume density g/cm 3 | 1.58 |
| Void content % | ＜26 | True density g/cm 3 | 2.07 |
The electrolyzer of potline current 200kA carries out electrolytic trial on the pre-baked carbon anode that obtains.
Ionogen is the sodium aluminum fluoride that contains Calcium Fluoride (Fluorspan), Sellaite and lithium fluoride, and wherein, the mass percent concentration of Calcium Fluoride (Fluorspan) is 4%, the mass percent concentration of Sellaite is 2%, the mass percent concentration of lithium fluoride is 1.5%, the molecular ratio 2.40 of sodium aluminum fluoride.The mass percent concentration of aluminum oxide is 2.5%.950 ℃ of electrolysis temperatures; Bath voltage 4.2V; 4.4 centimetres of pole spans.
After 120 hours, obtain aluminium titanium scandium alloy, the weight percent of aluminium titanium scandium alloy consists of: scandium 1.677%, titanium 1.121%, all the other be aluminium, and unavoidable impurities, Fe in the impurity＜0.15%, Si＜0.12%, and other impurity is micro-.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction; Though the present invention discloses as above with preferred embodiment; Yet be not in order to limiting the present invention, anyly be familiar with the professional and technical personnel, in not breaking away from technical scheme scope of the present invention; When the technology contents of above-mentioned announcement capable of using is made a little change or is modified to the equivalent embodiment of equivalent variations; In every case be the content that does not break away from technical scheme of the present invention, to any simple modification, equivalent variations and modification that above embodiment did, all still belong in the scope of technical scheme of the present invention according to technical spirit of the present invention.
Claims (8)
1. pre-baking carbon anode block, by in after-smithing petroleum coke, coal-tar pitch and the following oxide compound at least two kinds process: ZIRCONIUM DIOXIDE 99.5, scandium oxide and titanium oxide; By weight percentage, said after-smithing petroleum coke is 70～82%; Said coal-tar pitch is 15～28%; Said scandium oxide is 0～6%; Said ZIRCONIUM DIOXIDE 99.5 is 0～5%; Said titanium oxide is 0～5%.
2. pre-baking carbon anode block according to claim 1 is characterized in that:
Said pre-baking carbon anode block is processed by 72～81% said after-smithing petroleum cokes, 17% said coal-tar pitch, 1～6% said scandium oxide and 1～5% said ZIRCONIUM DIOXIDE 99.5.
3. pre-baking carbon anode block according to claim 1 is characterized in that:
Said pre-baking carbon anode block is processed by 75～81% said after-smithing petroleum cokes, 15～17% said coal-tar pitch, 1～5% said titanium oxide and 1～5% said ZIRCONIUM DIOXIDE 99.5.
4. pre-baking carbon anode block according to claim 1 is characterized in that:
Said pre-baking carbon anode block is processed by 74～81% said after-smithing petroleum cokes, 15～17% said coal-tar pitch, 1～6% said scandium oxide and 1～5% said titanium oxide.
5. pre-baking carbon anode block according to claim 1 is characterized in that:
Said pre-baking carbon anode block is processed by 70～82% said after-smithing petroleum cokes, 15～28% said coal-tar pitch, 0.5～5% said scandium oxide, 1～5% said titanium oxide and 0.5～5% said ZIRCONIUM DIOXIDE 99.5.
6. pre-baked carbon anode is the pre-baked carbon anode that arbitrary described pre-baking carbon anode block roasting in the claim 1 to 5 is obtained.
7. pre-baked carbon anode according to claim 6 is characterized in that:
The temperature of said roasting is 1150～1250 ℃, and the time is 600～720 hours.
8. method of producing duraluminum is to be anode with the described pre-baked carbon anode of claim 7, electrolysis of aluminum oxide for producing aluminum alloy in containing the ionogen of sodium aluminum fluoride; Also containing mass percent concentration in the said ionogen is 4～5% Calcium Fluoride (Fluorspan), 2～3% Sellaites and 1.5～2% lithium fluoride; The molecular ratio of said sodium aluminum fluoride is 2.2～2.6; The mass percent concentration of said aluminum oxide is 1.5～3.5%.
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| CN103454984B (en) * | 2012-05-31 | 2016-01-13 | 沈阳铝镁设计研究院有限公司 | Raw-anode carbon block quality influence analysis process control method |
| CN109763146B (en) * | 2019-03-27 | 2021-03-26 | 贵州省过程工业技术研究中心 | Preparation method of titanium-based composite material anode for aluminum electrolysis |
| CN112853403B (en) * | 2021-01-11 | 2021-12-07 | 山西沁新能源集团股份有限公司 | Prebaked anode, and preparation method and application thereof |
| CN114014659B (en) * | 2021-11-05 | 2022-12-13 | 新疆农六师碳素有限公司 | Novel high-end carbon product material for aluminum and preparation method thereof |
| CN115974556B (en) * | 2022-12-09 | 2023-09-19 | 中国铝业股份有限公司 | Preparation method of low-slag-drop prebaked anode and low-slag-drop prebaked anode |
| CN117004992B (en) * | 2023-08-17 | 2024-01-26 | 鞍山炭素有限公司 | Preparation method of high-strength graphite anode |
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