CN102703929A - 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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- CN102703929A CN102703929A CN2012101111816A CN201210111181A CN102703929A CN 102703929 A CN102703929 A CN 102703929A CN 2012101111816 A CN2012101111816 A CN 2012101111816A CN 201210111181 A CN201210111181 A CN 201210111181A CN 102703929 A CN102703929 A CN 102703929A
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- ilmenite
- alloy
- electrode
- prereduction
- electrolysis
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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
- 238000000034 method Methods 0.000 title claims abstract description 44
- 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
- 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 23
- 230000002829 reductive effect Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000463 material Substances 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
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 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
- 239000007788 liquid Substances 0.000 claims description 11
- 238000005453 pelletization Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 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 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 11
- 150000003839 salts Chemical class 0.000 description 10
- 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 7
- 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
- 150000002500 ions Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 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 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 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
- 239000007864 aqueous solution Substances 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
- 239000010959 steel Substances 0.000 description 3
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-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 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 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
- 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004070 electrodeposition Methods 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
- 150000002431 hydrogen Chemical class 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
- 239000000203 mixture Substances 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
- 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 the Non-ferrous Metallurgy field, the hot prereduction of particularly a kind of carbon combines with the ionic liquid electrolytic reduction and directly prepares the method for Ti-Fe alloy from ilmenite.
Background technology
Ferro-titanium is not only the important raw and processed materials in the smelting iron and steel, and still important magneticsubstance is developed one of hydrogen storage material of potential quality with tool, has the wide industrial purposes.As use ferro-titanium when making steel, and not only can improve the mechanical property of steel, can also improve its crystal structure.
Produce ferro-titanium at present and mainly adopt metallothermics (thermit reduction) and remelting process.Wherein thermit reduction is that concentrated ilmenite powder and aluminium powder, ferrosilicon are mixed respectively by a certain percentage; Then with the initiation reaction of magnesium powder and rely on id reaction heat to carry out redox and obtain ferro-titanium; But exist oxygen level higher, defective such as impurity is many is restricted the application of ferro-titanium.Remelting process is to be that main raw material adds the iron remelting with useless titanium material, generally adopts the induction furnace remelting, and also useful electrode arc stove is smelted or in the electric furnace of logical shielding gas, used the radiogenic heat melting.Adopt remelting process to prepare ferro-titanium and can control oxygen level in the alloy effectively, but its raw material sources are limited, energy dissipation is bigger, and cost is high, is difficult to meet the need of market.Therefore, be necessary to study flow process weak point, the low environment amenable preparation method of reaching of cost, ferro-titanium can be applied in more field.
For seeking new low cost titanium iron alloy preparation technology, all done number of research projects both at home and abroad.The novel process of research has fused salt electrolysis process etc.This method is at first with TiO
2And Fe
2O
3The negative electrode of mixed sintering adopts CaCl then
2The high-temperature molten salt system is a ferro-titanium with its electrolytic reduction as ionogen directly under 800～1000 ℃.Because this method is directly from TiO
2And Fe
2O
3The mixture electrolysis obtains ferro-titanium, has greatly simplified technical process and equipment.But up to the present this method just succeeds in the laboratory, realize scale operation, at first will solve TiO
2And Fe
2O
3Mixed cathode preparation and the bad problem of electroconductibility, the airtight and atmosphere protection of its less important realization electrolyzer also must overcome in the electrolytic process titanium ion variation of valence then to the influence of current efficiency.To overcome the above problems simultaneously, also have very big difficulty in practice.And fused salt electrolysis will be carried out needs consumption certain energy and etching apparatus under 800 ℃ temperature.Therefore, press for simple, energy-conservation, the titanium new preparation technology cheaply of a kind of technology of development, ion liquid appearance provides new possibility undoubtedly for this reason.
Ionic liquid is the abbreviation of ionic liquid at room temperature, is a kind ofly to be made up of near the organic salt that room temperature or room temperature, is in a liquid state the yin, yang ion.It has excellent properties such as electrochemical window is wide, good conductivity, liquid wide ranges, no vp, good stability, is a kind of green solvent.Aspect galvanic deposit; Ionic liquid has merged the advantage of the high-temperature molten salt and the aqueous solution: electrochemical window and good electrical conductivity with broad; At room temperature can obtain the ability galvanic deposit goes out in high-temperature molten salt metal and alloy, but not have the such severe corrosive of high-temperature molten salt; Simultaneously; In ionic liquid, go back electrodepositable and obtain most of metals that can in the aqueous solution, obtain, and do not have side reaction, thereby the metal quality that obtains is better; Current efficiency is higher, and it is all the more so particularly aluminium, titanium, silicon and germanium etc. to be difficult in metal and alloy thereof that aqueous solution electrodeposition obtains.Ion liquid above-mentioned characteristic and good specific conductivity thereof make it to become the brand-new liquid of galvanic deposit research, aspect electrodeposit metals, obtain increasing application.
Summary of the invention
The invention provides and a kind ofly prepare the method for Ti-Fe alloy based on carbon hot in-place prereduction-ionic liquid electrolytic reduction; Its purpose is to solve metallothermy and prepares the ferro-titanium too high oxygen level, has satisfied not customer need and problems such as the remelting process raw material sources are few, energy consumption is big, cost height.
The present invention realizes through following technical scheme: the method for Ti-Fe alloy is produced in the direct reduction of a kind of ilmenite; The prereduction of carbon hot in-place and the ionic liquid electrolysis prereduction ilmenite that comprise ilmenite prepare two steps of ferro-titanium, specifically pass through following each step:
(1) with the ilmenite be raw material, carbon dust is a reductive agent, calcines 0.5～4h down at 1000～1200 ℃ and processes prereduction ilmenite electrode;
(2) with the ionic liquid be ionogen; With step (1) gained prereduction ilmenite electrode is negative electrode; With graphite or other inert material is anode, is that 2.8～3.2V, electrolysis temperature are to carry out electrolysis under 25～120 ℃ 12～48 hours at electrolysis voltage, takes out negative electrode then; After flushing and drying, promptly obtain the Ti-Fe alloy.
Said step (1) specifically be with ilmenite powder, to account for the ilmenite powder mass percent be 7～16% carbon dust and to account for the ilmenite powder mass percent be that 1～2% PVA sticker mixes; Be pressed into bulk again, in reducing atmosphere, calcine 1～4h down then and process blocky prereduction ilmenite electrode in 1000～1200 ℃.
Said step (1) specifically is with ilmenite powder, water and to account for the ilmenite powder mass percent be that 7～16% carbon dust mixes; Wherein water accounts for 6～10% of compound total mass; Process the pelletizing that diameter is 1～10mm again; Then in reducing atmosphere in 1000～1200 ℃ of following calcining 0.5～2h, pelletizing is packed into process prereduction ilmenite electrode in the porous container with electroconductibility at last.
The electrolytic solution of said step (2) is glyoxaline ion liquid, pyridines ionic liquid, quaternary phosphine salt ionic liquid or ion liquid of quaternaries.
Glyoxaline ion liquid wherein is like 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-methyl imidazolium tetrafluoroborate ([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 HFC-227 sulphonate ([Bmim] C
3F
7SO
3 -), 1-ethyl-3-Methylimidazole HFC-227 sulphonate ([Emim] C
3F
7SO
3 -);
The pyridines ionic liquid is like two fluoroform sulfimide salt ([bPy] NTf of N-butyl-pyridinium
2);
Quaternary phosphine salt ionic liquid is like two fluoroform sulfimide the salt ([P of tributyl tetradecyl phosphine
14,444] NTf
2);
Ion liquid of quaternaries is like two fluoroform sulfimide the salt ([N of tetramethyl-ammonium
1111] NTf
2).
Said reducing atmosphere is for containing reducing gas (like carbon monoxide, hydrogen, methane, ammonia etc.) gas (flue gas) atmosphere that oxygen level is very low.
Effect that the present invention possesses and advantage: this method directly is converted into the Ti-Fe alloy with ilmenite, and the Ti-Fe alloy oxygen level that obtains is lower, and the electrolytic reduction temperature is low.Compare with existing Ti-Fe alloy preparation method, the present invention has shortened technical process, has greatly reduced energy consumption, and the quality product that obtains is high.
Advantages such as at first, the present invention is to be starting material with the ilmenite, and it is wide to have raw material sources, and production cost is low, this point is compared 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; The 3rd; Electrolytic reduction temperature of the present invention is low, and the present invention adopts ionic liquid electrolytic reduction temperature below 100 ℃, and the high temperature fused salt electrolysis temperature is more than 800 ℃; Reduced by 700 ℃, practiced thrift cost to a great extent, reduced energy consumption and slowed down corrosion on Equipment; The 4th, because the electroconductibility of ilmenite is relatively poor, use ilmenite under carbon reduction atmosphere, to reduce calcining as raw material, make the iron in the ilmenite be reduced to metallographic phase, improve the electroconductibility of negative electrode, the electrochemical deoxidising efficient in the raising electrolytic process; Negative electrode adopts the spheroidal particle structure, and further fast reaction speed improves deoxidation efficient.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
(1) with the ilmenite is raw material; Carbon dust is a reductive agent; With ilmenite powder, to account for the ilmenite powder mass percent be 12% carbon dust and to account for the ilmenite powder mass percent be that 2% PVA sticker mixes; Be pressed into bulk again, in reducing atmosphere, calcine 4h down then and process blocky prereduction ilmenite electrode in 1000 ℃;
(2) with alkalescence [Bmim] Cl-AlCl
3Ionic liquid is an ionogen, is negative electrode with step (1) gained prereduction ilmenite electrode, is anode with graphite or other inert material; At electrolysis voltage is that 3.0V, electrolysis temperature are to carry out electrolysis under 80 ℃ 14 hours; Take out negative electrode then, after flushing and drying, promptly obtain the Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 600ppm.
Embodiment 2
(1) with the ilmenite is raw material; Carbon dust is a reductive agent; With ilmenite powder, water with to account for the ilmenite powder mass percent be that 7% carbon dust mixes, wherein water accounts for 10% of compound total mass, processes the pelletizing that diameter is 2mm again; Then in the reducing atmosphere carbon monoxide in 1000 ℃ of following calcining 2h, pelletizing is packed into process prereduction ilmenite electrode in the mesh 120 purpose titanium nets with electroconductibility at last;
(2) with [Bmim] PF
6Ionic liquid is an ionogen, is negative electrode with step (1) gained prereduction ilmenite electrode, is anode with graphite or other inert material; At electrolysis voltage is that 3V, electrolysis temperature are to carry out electrolysis under 100 ℃ 14 hours; Take out negative electrode then, after flushing and drying, promptly obtain the Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 500ppm.
Embodiment 3
(1) with the ilmenite is raw material; Carbon dust is a reductive agent; With ilmenite powder, water with to account for the ilmenite powder mass percent be that 10% carbon dust mixes, wherein water accounts for 6% of compound total mass, processes the pelletizing that diameter is 1mm again; Then in reducing atmosphere in 1100 ℃ of following calcining 1h, pelletizing is packed into process prereduction ilmenite electrode in the mesh 200 purpose titanium nets with electroconductibility at last;
(2) with [Bmim] NTf
2Ionic liquid is an ionogen, is negative electrode with step (1) gained prereduction ilmenite electrode, is anode with graphite or other inert material; At electrolysis voltage is that 2.8V, electrolysis temperature are to carry out electrolysis under 25 ℃ 16 hours; Take out negative electrode then, after flushing and drying, promptly obtain the Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 500ppm.
Embodiment 4
(1) with the ilmenite is raw material; Carbon dust is a reductive agent; With ilmenite powder, water with to account for the ilmenite powder mass percent be that 16% carbon dust mixes, wherein water accounts for 8% of compound total mass, processes the pelletizing that diameter is 10mm again; Then in reducing atmosphere hydrogen in 1200 ℃ of following calcining 0.5h, pelletizing is packed into process prereduction ilmenite electrode in the mesh 100 purpose titanium nets with electroconductibility at last;
(2) with [N
1111] NTf
2Ionic liquid is an ionogen, is negative electrode with step (1) gained prereduction ilmenite electrode, is anode with graphite or other inert material; At electrolysis voltage is that 2.8V, electrolysis temperature are to carry out electrolysis under 100 ℃ 16 hours; Take out negative electrode then, after flushing and drying, promptly obtain the Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 400ppm.
Embodiment 5
(1) with the ilmenite is raw material; Carbon dust is a reductive agent; With ilmenite powder, to account for the ilmenite powder mass percent be 7% carbon dust and to account for the ilmenite powder mass percent be that 1% PVA sticker mixes; Be pressed into bulk again, in reducing atmosphere, calcine 2h down then and process blocky prereduction ilmenite electrode in 1200 ℃;
(2) with [bPy] NTf
2Ionic liquid is an ionogen, is negative electrode with step (1) gained prereduction ilmenite electrode, is anode with graphite or other inert material; At electrolysis voltage is that 3.2V, electrolysis temperature are to carry out electrolysis under 60 ℃ 12 hours; Take out negative electrode then, after flushing and drying, promptly obtain the Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 500ppm.
Embodiment 6
(1) with the ilmenite is raw material; Carbon dust is a reductive agent; With ilmenite powder, to account for the ilmenite powder mass percent be 16% carbon dust and to account for the ilmenite powder mass percent be that 2% PVA sticker mixes; Be pressed into bulk again, in reducing atmosphere, calcine 1h down then and process blocky prereduction ilmenite electrode in 1100 ℃;
(2) with [P
14,444] NTf
2Ionic liquid is an ionogen, is negative electrode with step (1) gained prereduction ilmenite electrode, is anode with graphite or other inert material; At electrolysis voltage is that 2.9V, electrolysis temperature are to carry out electrolysis under 120 ℃ 48 hours; Take out negative electrode then, after flushing and drying, promptly obtain the Ti-Fe alloy.The oxygen level of Ti-Fe alloy is lower than 400ppm.
Claims (4)
- An ilmenite directly reduction produce the method for Ti-Fe alloy, it is characterized in that specifically passing through following each step:(1) with the ilmenite be raw material, carbon dust is a reductive agent, calcines 0.5～4h down at 1000～1200 ℃ and processes prereduction ilmenite electrode;(2) with the ionic liquid be ionogen; With step (1) gained prereduction ilmenite electrode is negative electrode; With graphite or other inert material is anode, is that 2.8～3.2V, electrolysis temperature are to carry out electrolysis under 25～120 ℃ 12～48 hours at electrolysis voltage, takes out negative electrode then; After flushing and drying, promptly obtain the Ti-Fe alloy.
- 2. the method for Ti-Fe alloy is produced in the direct reduction of a kind of ilmenite according to claim 1; It is characterized in that: said step (1) specifically be with ilmenite powder, to account for the ilmenite powder mass percent be 7～16% carbon dust and to account for the ilmenite powder mass percent be that 1～2% PVA sticker mixes; Be pressed into bulk again, in reducing atmosphere, calcine 1～4h down then and process blocky prereduction ilmenite electrode in 1000～1200 ℃.
- 3. the method for Ti-Fe alloy is produced in the direct reduction of a kind of ilmenite according to claim 1; It is characterized in that: said step (1) specifically is with ilmenite powder, water and to account for the ilmenite powder mass percent be that 7～16% carbon dust mixes; Wherein water accounts for 6～10% of compound total mass; Process the pelletizing that diameter is 1～10mm again; Then in reducing atmosphere in 1000～1200 ℃ of following calcining 0.5～2h, pelletizing is packed into process prereduction ilmenite electrode in the porous container with electroconductibility at last.
- 4. the method for Ti-Fe alloy is produced in the direct reduction of a kind of ilmenite according to claim 1, and it is characterized in that: the electrolytic solution of said step (2) is glyoxaline ion liquid, pyridines ionic liquid, quaternary phosphine salt ionic liquid or ion liquid of quaternaries.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103343373A (en) * | 2013-07-06 | 2013-10-09 | 哈尔滨工业大学 | Preparation method of ionic liquid electrodeposition copper/indium/gallium/selenium CIGS thin-film materials |
| 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 |
| CN104213151A (en) * | 2014-09-05 | 2014-12-17 | 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 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385397A (en) * | 2002-04-23 | 2002-12-18 | 重庆大学 | Technological method for preparing TiX (X=c,N) compound powder by direct reducing washingtonite |
| CN101994128A (en) * | 2010-11-26 | 2011-03-30 | 昆明理工大学 | Method for preparing Al-Ti alloy or plated Al-Ti alloy by low-temperature electrolytic deposition of ionic liquid |
-
2012
- 2012-04-17 CN CN201210111181.6A patent/CN102703929B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385397A (en) * | 2002-04-23 | 2002-12-18 | 重庆大学 | Technological method for preparing TiX (X=c,N) compound powder by direct reducing washingtonite |
| CN101994128A (en) * | 2010-11-26 | 2011-03-30 | 昆明理工大学 | Method for preparing Al-Ti alloy or plated Al-Ti alloy by low-temperature electrolytic deposition of ionic liquid |
Non-Patent Citations (2)
| Title |
|---|
| XIAO-YING ZHANG ET AL.: "Direct electrochemical reduction of titanium dioxide in Lewis basic", 《ELECTROCHIMICA ACTA》, vol. 56, 22 July 2011 (2011-07-22) * |
| 刘许旸等: "熔盐电解钛精矿制备钛铁合金的脱氧历程", 《功能材料》, vol. 42, no. 11, 30 November 2011 (2011-11-30) * |
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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 |
| CN104213151A (en) * | 2014-09-05 | 2014-12-17 | 昆明理工大学 | Method for preparing lead-antimony alloy by directly electrolyzing lead-antimony oxide |
| 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 |
| CN106811563A (en) * | 2015-12-02 | 2017-06-09 | 鞍钢股份有限公司 | A kind of method that application electric field carries out iron ore reduction ironmaking |
| 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 |
| CN115518627A (en) * | 2022-09-21 | 2022-12-27 | 四川师范大学 | Preparation method and application of defect perovskite type catalyst |
| 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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