CN102703929B - Method for preparing Ti-Fe alloy by direct reduction of ilmenite - Google Patents
Method for preparing Ti-Fe alloy by direct reduction of ilmenite Download PDFInfo
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- CN102703929B CN102703929B CN201210111181.6A CN201210111181A CN102703929B CN 102703929 B CN102703929 B CN 102703929B CN 201210111181 A CN201210111181 A CN 201210111181A CN 102703929 B CN102703929 B CN 102703929B
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- ionic liquid
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- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 34
- 239000000956 alloy Substances 0.000 title claims abstract description 34
- 229910011212 Ti—Fe Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000002829 reductive effect Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000000428 dust Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005453 pelletization Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 8
- -1 glyoxaline ion Chemical class 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 5
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- DVYSHWKJRYAQOJ-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;2,2,2-trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.CCCCN1CN(C)C=C1 DVYSHWKJRYAQOJ-UHFFFAOYSA-N 0.000 description 1
- SFPTVQNKTCPLAX-UHFFFAOYSA-N 3-ethyl-1-methyl-1,2-dihydroimidazol-1-ium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CC[NH+]1CN(C)C=C1 SFPTVQNKTCPLAX-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JMNFVQWMBCLWAS-UHFFFAOYSA-N C(F)(F)F.C(C)N1CN(C=C1)C Chemical compound C(F)(F)F.C(C)N1CN(C=C1)C JMNFVQWMBCLWAS-UHFFFAOYSA-N 0.000 description 1
- DYVIVMCAMDJZLM-UHFFFAOYSA-N C(F)(F)F.C(CCC)N1CN(C=C1)C Chemical compound C(F)(F)F.C(CCC)N1CN(C=C1)C DYVIVMCAMDJZLM-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XHIHMDHAPXMAQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XHIHMDHAPXMAQK-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a method for preparing Ti-Fe alloy by direct reduction of ilmenite, which comprises the steps of: based on ilmenite as a raw material and carbon powder as a reducing agent, calcining at 1000-1200 DEG C for 0.5-4h to prepare a pre-reduced ilmenite electrode, carrying out electrolysis at the electrolysis voltage of 2.8-3.2V and electrolysis temperature of 25-120 DEG C with an ionic liquid as the electrolyte, the obtained pre-reduced ilmenite electrode as the cathode and graphite or other inert materials as the anode for 12-48h, then taking out the cathode, washing and drying to obtain the Ti-Fe alloy. The obtained Ti-Fe alloy has lower oxygen content; and compared with the traditional Ti-Fe alloy preparation method, the method has the advantages that the process flow is shortened, the energy consumption is greatly reduced and clean production is realized.
Description
Technical field
The invention belongs to Non-ferrous Metallurgy field, particularly the hot prereduction of a kind of carbon combines with ionic liquid electrolytic reduction and directly prepares the method for Ti-Fe alloy from ilmenite.
Background technology
One of the important raw and processed materials in smelting iron and steel is not only by ferro-titanium, or the hydrogen storage material of important magneticsubstance and most exploitation potential quality, there is industrial use widely.Using ferro-titanium during as made steel, not only can improve the mechanical property of steel, its crystal structure can also be improved.
Current production ferro-titanium mainly adopts metallothermics (thermit reduction) and remelting process.Wherein thermit reduction is mixed by a certain percentage respectively concentrated ilmenite powder and aluminium powder, ferrosilicon, then id reaction heat is relied on to carry out redox and obtain ferro-titanium with the initiation reaction of magnesium powder, but it is higher to there is oxygen level, the defects such as impurity is many, make the application of ferro-titanium be restricted.Remelting process is with useless titanium material for main raw material adds iron remelting, and the remelting of general employing induction furnace, also useful electrode arc stove is smelted or in the electric furnace of logical shielding gas, used radiant heat melting.Adopt remelting process to prepare ferro-titanium and can effectively control oxygen level in alloy, but its raw material sources are limited, energy dissipation is comparatively large, and cost is high, is difficult to meet the need of market.Therefore, be necessary that research flow process is short, cost is low and environment amenable preparation method, and ferro-titanium can be applied in more field.
For seeking new low cost titanium iron alloy preparation technology, all do a large amount of research work both at home and abroad.The novel process of research has fused salt electrolysis process etc.The method is first by TiO
2and Fe
2o
3the negative electrode of mixed sintering, then adopts CaCl
2high-temperature molten salt system is as ionogen, and direct at 800 ~ 1000 DEG C is ferro-titanium by its electrolytic reduction.Because this method is directly from TiO
2and Fe
2o
3mixture electrolysis obtains ferro-titanium, greatly simplifies technical process and equipment.But up to the present the method just succeeds in laboratory, realize scale operation, first will solve TiO
2and Fe
2o
3the preparation of mixing negative electrode and the bad problem of electroconductibility, it is secondary realizes the airtight of electrolyzer and atmosphere protection, then also must to overcome in electrolytic process titanium ion variation of valence to the impact of current efficiency.To overcome the above problems simultaneously, also have very large difficulty in practice.And fused salt electrolysis will be carried out at the temperature of 800 DEG C, need to consume certain energy and etching apparatus.Therefore, in the urgent need to developing, a kind of technique is simple, energy-conservation, the titanium new preparation technology of low cost, and the appearance of ionic liquid is undoubtedly for herein is provided new possibility.
Ionic liquid is the abbreviation of ionic liquid at room temperature, is a kind of composition anions and canons, at the organic salt that room temperature or near room temperature are in a liquid state.It has that electrochemical window is wide, good conductivity, liquid state range are wide, without the excellent properties such as vapour pressure, good stability, be a kind of green solvent.In galvanic deposit, ionic liquid has merged the advantage of high-temperature molten salt and the aqueous solution: have wider electrochemical window and good electroconductibility, at room temperature can obtain in high-temperature molten salt could the metal that goes out of galvanic deposit and alloy, but the severe corrosive not having high-temperature molten salt such; Simultaneously, in ionic liquid, go back electrodepositable obtain most of metal that can obtain in aqueous, and without side reaction, the metal quality thus obtained is better, current efficiency is higher, particularly to aluminium, titanium, silicon and germanium etc. be difficult in aqueous the metal that obtains of galvanic deposit and alloy all the more so.The above-mentioned characteristic of ionic liquid and good specific conductivity thereof make it the brand-new liquid becoming galvanic deposit research, are more and more applied in electrodeposit metals.
Summary of the invention
The invention provides a kind of method preparing Ti-Fe alloy based on carbon hot in-place prereduction-ionic liquid electrolytic reduction, its object is to solve metallothermic reduction and prepare ferro-titanium too high oxygen level, can not meet customer need and remelting process raw material sources are few, energy consumption is large, high in cost of production problem.
The present invention is achieved through the following technical solutions: a kind of ilmenite direct-reduction produces the method for Ti-Fe alloy, the prereduction of carbon hot in-place and the ionic liquid electrolysis prereduction ilmenite that comprise ilmenite prepare ferro-titanium two steps, specifically through following each step:
(1) take ilmenite as raw material, carbon dust is reductive agent, calcines 0.5 ~ 4h and make prereduction ilmenite electrode at 1000 ~ 1200 DEG C;
(2) take ionic liquid as ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 2.8 ~ 3.2V, electrolysis temperature carries out electrolysis 12 ~ 48 hours at being 25 ~ 120 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.
Described step (1) specifically by ilmenite powder, account for ilmenite powder mass percent be 7 ~ 16% carbon dust and account for ilmenite powder mass percent be 1 ~ 2% PVA binding agent mix, be pressed into bulk again, in reducing atmosphere, at 1000 ~ 1200 DEG C, then calcine 1 ~ 4h make block prereduction ilmenite electrode.
Described step (1) specifically by ilmenite powder, water and account for ilmenite powder mass percent be 7 ~ 16% carbon dust mix, wherein water accounts for 6 ~ 10% of compound total mass, make the pelletizing that diameter is 1 ~ 10mm again, then in reducing atmosphere, at 1000 ~ 1200 DEG C, calcine 0.5 ~ 2h, finally pelletizing is loaded in the porous container with electroconductibility and make prereduction ilmenite electrode.
The electrolytic solution of described step (2) is glyoxaline ion liquid, pyridine ionic liquid, quaternary phosphine salt ionic liquid or ion liquid of quaternaries.
Wherein glyoxaline ion liquid, as alkaline chloro 1-butyl-3-Methylimidazole-aluminum chloride (BmimCl-AlCl
3), alkaline chloro 1-ethyl-3-methylimidazole-aluminum chloride (EmimCl-AlCl
3), 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] BF
4), 1-ethyl-3-methylimidazole a tetrafluoro borate ([Emim] BF
4), 1-butyl-3-Methylimidazole hexafluorophosphate ([Bmim] PF
6), 1-ethyl-3-methylimidazole hexafluorophosphate ([Emim] PF
6), two fluoroform sulfimide salt ([Bmim] NTf of 1-butyl-3-Methylimidazole fluoroform sulphonate ([Bmim] OTf), 1-ethyl-3-methylimidazole fluoroform sulphonate ([Emim] OTf), 1-butyl-3-Methylimidazole
2), two fluoroform sulfimide salt ([Emim] NTf of 1-ethyl-3-methylimidazole
2), 1-butyl-3-Methylimidazole trifluoroacetate ([Bmim] CF
3cOO
-), 1-ethyl-3-methylimidazole trifluoroacetate ([Emim] CF
3cOO
-), 1-butyl-3-Methylimidazole heptafluoro-propane sulfonate ([Bmim] C
3f
7sO
3 -), 1-ethyl-3-methylimidazole heptafluoro-propane sulfonate ([Emim] C
3f
7sO
3 -);
Pyridine ionic liquid, fluoroform sulfimide salt ([bPy] NTf as two in N-butyl-pyridinium
2);
Quaternary phosphine salt ionic liquid, fluoroform sulfimide salt ([P as two in tributyl tetradecyl phosphine
14,444] NTf
2);
Ion liquid of quaternaries, fluoroform sulfimide salt ([N as two in tetramethyl-ammonium
1111] NTf
2).
Described reducing atmosphere is very low gas (flue gas) atmosphere of oxygen level containing reducing gas (as carbon monoxide, hydrogen, methane, ammonia etc.).
The effect that the present invention possesses and advantage: ilmenite is directly converted into Ti-Fe alloy by the method, the Ti-Fe alloy oxygen level obtained is lower, and electrolytic reduction temperature is low.Compared with existing Ti-Fe alloy preparation method, present invention reduces technical process, significantly reduce energy consumption, the quality product obtained is high.
First, the present invention is starting material with ilmenite, has raw material sources wide, the advantages such as production cost is low, and this point compares the progress with essence with traditional iron remelting that adds with vacuum melting; Secondly, it is lower that the present invention can directly obtain oxygen level, the high-quality Ti-Fe alloy that purity is higher; 3rd, electrolytic reduction temperature of the present invention is low, and the present invention adopts ionic liquid electrolytic reduction temperature below 100 DEG C, and high temperature fused salt electrolysis temperature is more than 800 DEG C, reduce 700 DEG C, to a great extent cost-saving, reduce energy consumption and slow down the corrosion to equipment; 4th, because the electroconductibility of ilmenite is poor, use ilmenite under carbon reducing atmosphere, reduce calcining for raw material, make the Fe3+ reduction in ilmenite be metallographic phase, improve the electroconductibility of negative electrode, the electrochemical deoxidising efficiency in raising electrolytic process; Negative electrode adopts spheroidal particle structure, can fast reaction speed further, raising deoxidation effectiveness.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) take ilmenite as raw material, carbon dust is reductive agent, by ilmenite powder, account for ilmenite powder mass percent be 12% carbon dust and account for ilmenite powder mass percent be 2% PVA binding agent mix, be pressed into bulk again, in reducing atmosphere, at 1000 DEG C, then calcine 4h make block prereduction ilmenite electrode;
(2) with alkalescence [Bmim] Cl-AlCl
3ionic liquid is ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 3.0V, electrolysis temperature carries out electrolysis 14 hours at being 80 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 600ppm.
Embodiment 2
(1) take ilmenite as raw material, carbon dust is reductive agent, by ilmenite powder, water and account for ilmenite powder mass percent be 7% carbon dust mix, wherein water accounts for 10% of compound total mass, make the pelletizing that diameter is 2mm again, then in reducing atmosphere carbon monoxide, at 1000 DEG C, calcine 2h, finally pelletizing is loaded in the mesh 120 object titanium net with electroconductibility and make prereduction ilmenite electrode;
(2) with [Bmim] PF
6ionic liquid is ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 3V, electrolysis temperature carries out electrolysis 14 hours at being 100 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 500ppm.
Embodiment 3
(1) take ilmenite as raw material, carbon dust is reductive agent, by ilmenite powder, water and account for ilmenite powder mass percent be 10% carbon dust mix, wherein water accounts for 6% of compound total mass, make the pelletizing that diameter is 1mm again, then in reducing atmosphere, at 1100 DEG C, calcine 1h, finally pelletizing is loaded in the mesh 200 object titanium net with electroconductibility and make prereduction ilmenite electrode;
(2) with [Bmim] NTf
2ionic liquid is ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 2.8V, electrolysis temperature carries out electrolysis 16 hours at being 25 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 500ppm.
Embodiment 4
(1) take ilmenite as raw material, carbon dust is reductive agent, by ilmenite powder, water and account for ilmenite powder mass percent be 16% carbon dust mix, wherein water accounts for 8% of compound total mass, make the pelletizing that diameter is 10mm again, then in reducing atmosphere hydrogen, at 1200 DEG C, calcine 0.5h, finally pelletizing is loaded in the mesh 100 object titanium net with electroconductibility and make prereduction ilmenite electrode;
(2) with [N
1111] NTf
2ionic liquid is ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 2.8V, electrolysis temperature carries out electrolysis 16 hours at being 100 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 400ppm.
Embodiment 5
(1) take ilmenite as raw material, carbon dust is reductive agent, by ilmenite powder, account for ilmenite powder mass percent be 7% carbon dust and account for ilmenite powder mass percent be 1% PVA binding agent mix, be pressed into bulk again, in reducing atmosphere, at 1200 DEG C, then calcine 2h make block prereduction ilmenite electrode;
(2) with [bPy] NTf
2ionic liquid is ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 3.2V, electrolysis temperature carries out electrolysis 12 hours at being 60 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 500ppm.
Embodiment 6
(1) take ilmenite as raw material, carbon dust is reductive agent, by ilmenite powder, account for ilmenite powder mass percent be 16% carbon dust and account for ilmenite powder mass percent be 2% PVA binding agent mix, be pressed into bulk again, in reducing atmosphere, at 1100 DEG C, then calcine 1h make block prereduction ilmenite electrode;
(2) with [P
14,444] NTf
2ionic liquid is ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 2.9V, electrolysis temperature carries out electrolysis 48 hours at being 120 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 400ppm.
Claims (4)
1. ilmenite direct-reduction produces a method for Ti-Fe alloy, it is characterized in that specifically through following each step:
(1) take ilmenite as raw material, carbon dust is reductive agent, calcines 0.5 ~ 4h and make prereduction ilmenite electrode at 1000 ~ 1200 DEG C;
(2) take ionic liquid as ionogen, with step (1) gained prereduction ilmenite electrode for negative electrode, with graphite or other inert material for anode, electrolysis voltage be 2.8 ~ 3.2V, electrolysis temperature carries out electrolysis 12 ~ 48 hours at being 25 ~ 120 DEG C, then negative electrode is taken out, through rinsing and after drying, namely obtaining Ti-Fe alloy.
2. a kind of ilmenite direct-reduction according to claim 1 produces the method for Ti-Fe alloy, it is characterized in that: described step (1) specifically by ilmenite powder, account for ilmenite powder mass percent be 7 ~ 16% carbon dust and account for ilmenite powder mass percent be 1 ~ 2% PVA binding agent mix, be pressed into bulk again, in reducing atmosphere, at 1000 ~ 1200 DEG C, then calcine 1 ~ 4h make block prereduction ilmenite electrode.
3. a kind of ilmenite direct-reduction according to claim 1 produces the method for Ti-Fe alloy, it is characterized in that: described step (1) specifically by ilmenite powder, water and account for ilmenite powder mass percent be 7 ~ 16% carbon dust mix, wherein water accounts for 6 ~ 10% of compound total mass, make the pelletizing that diameter is 1 ~ 10mm again, then in reducing atmosphere, at 1000 ~ 1200 DEG C, calcine 0.5 ~ 2h, finally pelletizing is loaded in the porous container with electroconductibility and make prereduction ilmenite electrode.
4. a kind of ilmenite direct-reduction according to claim 1 produces the method for Ti-Fe alloy, it is characterized in that: the ionic liquid of described step (2) is glyoxaline ion liquid, pyridine ionic liquid, quaternary phosphine salt ionic liquid or ion liquid of quaternaries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN104131312A (en) * | 2014-07-08 | 2014-11-05 | 昆明理工大学 | Method utilizing eutectic solvent to carry out in-situ reduction on lead oxide to produce lead |
| CN104213151B (en) * | 2014-09-05 | 2017-05-10 | 昆明理工大学 | Method for preparing lead-antimony alloy by directly electrolyzing lead-antimony oxide |
| CN104499002A (en) * | 2014-12-10 | 2015-04-08 | 上海大学 | Method for preparing copper-iron nano plated layer from low-grade sulfide ore through direct electro-deposition |
| CN106811563B (en) * | 2015-12-02 | 2019-02-26 | 鞍钢股份有限公司 | A method of iron ore reduction ironmaking is carried out using electric field |
| CN110055366A (en) * | 2019-04-11 | 2019-07-26 | 东北大学 | A method of ferro-titanium is directly smelted using ilmenite |
| CN115518627B (en) * | 2022-09-21 | 2023-10-13 | 四川师范大学 | Preparation method and application of defect perovskite type catalyst |
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