CN107208184A - Method and apparatus for preparing the slag containing titanium oxide and the pig iron by ilmenite - Google Patents
Method and apparatus for preparing the slag containing titanium oxide and the pig iron by ilmenite Download PDFInfo
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- CN107208184A CN107208184A CN201680006936.2A CN201680006936A CN107208184A CN 107208184 A CN107208184 A CN 107208184A CN 201680006936 A CN201680006936 A CN 201680006936A CN 107208184 A CN107208184 A CN 107208184A
- Authority
- CN
- China
- Prior art keywords
- ilmenite
- prereduction
- electric arc
- arc furnaces
- reducing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 123
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002893 slag Substances 0.000 title claims abstract description 85
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910000805 Pig iron Inorganic materials 0.000 title claims abstract description 45
- 238000010891 electric arc Methods 0.000 claims abstract description 105
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 102
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 37
- 230000009467 reduction Effects 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 238000001465 metallisation Methods 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 239000003610 charcoal Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003830 anthracite Substances 0.000 claims description 7
- 238000002955 isolation Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 38
- 239000000463 material Substances 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 23
- 238000003860 storage Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 239000000571 coke Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 10
- 238000007499 fusion processing Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 229910009973 Ti2O3 Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000019771 cognition Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910005451 FeTiO3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910009815 Ti3O5 Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005138 cryopreservation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- -1 titanium oxides Compound Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B11/00—Making pig-iron other than in blast furnaces
- C21B11/10—Making pig-iron other than in blast furnaces in electric furnaces
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/006—Starting from ores containing non ferrous metallic oxides
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
- C21B13/143—Injection of partially reduced ore into a molten bath
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/52—Manufacture of steel in electric furnaces
- C21C5/54—Processes yielding slags of special composition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/08—Apparatus
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/18—Reducing step-by-step
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/08—Making spongy iron or liquid steel, by direct processes in rotary furnaces
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to the method for preparing the slag containing titanium oxide and the pig iron by ilmenite.The method is characterized in that it comprises the following steps：A) in prereduction reactor in the presence of a reducing agent prereduction ilmenite so that at least part ferrous metal in ilmenite；B) unreacted reducing agent and gangue optionally are removed from the ilmenite of prereduction；And c) in electric arc furnaces the pig iron so that titanium oxide is separated into melted gangue phase and is separated into molten metal phase by the ilmenite of melting prereduction.The invention further relates to for preparing the equipment of the slag containing titanium oxide and the pig iron by ilmenite, and it is related to slag and the pig iron containing titanium oxide.
Description
Technical field
Present disclosure is related to the method for preparing the slag containing titanium oxide and the pig iron by ilmenite melting
And equipment.
Background technology
Melting ilmenite is the main method for preparing the slag containing titanium oxide in electric arc furnaces.The name of ilmenite
Justice composition is FeTiO3Or FeO.TiO2.In the method, melting ilmenite is come by using electric energy.From furnace roof by ilmenite and
The mixture of carbon containing reducer (such as coke or coal) is continuously supplied into molten bath.
In fusion process, the ferriferous oxide that be will be present in by the carbon present in reducing agent in ilmenite is reduced into gold
Attribute form.This produces the slag containing titanium oxide with high titanium oxide content and low ferriferous oxide content.From stove
Bottom collection metallicity iron is used as the pig iron.The slag containing titanium oxide typically is sold into pigment production person is used at downstream
The slag (is wherein processed into pure TiO by reason2Pigment).
The following is two fundamental reactions in ilmenite melting：
The reduction of FeO from slag：
FeO+C→Fe+CO (1)
TiO in slag2Partial reduction：
TiO2+1/2C→TiO1.5+1/2CO (2)
Reaction (1) is carried out more to the right than reaction (2).The reduction reaction occurred in fusion process is highly endothermic.Cause
This method of smelting is unusual energy-intensive.When the direct melting using ilmenite, ash and gangue from reducing agent
Enter the slag containing titanium oxide with the other impurities in ore, reduce its TiO2Content simultaneously potentially limits its processing replacement
Scheme.
US 3765868A, which are disclosed, to be used for from ilmenite ore selective recovery metallicity iron and titanium oxide useful component
(value) method.This method includes reducing in particular type by heating in the presence of ferriferous oxide go back original reagent
Ilmenite ore and reduzate is separated into magnetic and nonmagnetic portion.By being heated to greater than about 1730 DEG C of temperature,
Electric arc melting of the magnetic part experience added with carbon in particle form.Gained molten ironlayer and fluid slag layer are separated.
The fluid slag includes at least about 93.5% TiO2No more than 6.3% FeO.
US 6306195B1 disclose the method for preparing high-grade titania by ilmenite, with pig iron conduct
Accessory substance.This method includes making ilmenite be subjected to the reduction using coal, cools down and removes unreacted coal to obtain with 80-
The product of 95% metallization, fixed duration melts in the transferred-arc plasma using arc current under the inert gas stream
Refining is mixed with the ilmenite of the metallization less than 10% (w/w) carbon, and the TiO using the metal as the pig iron and as slag2Point
From.
WO 2006048283A1 disclose the method and apparatus for preparing titanium dioxide slag by ilmenite.At least
The granular ilmenite of partial reduction in reduction reactor at a temperature of 900 DEG C.The ilmenite of prereduction is transferred in electric furnace (its
The inlet temperature of the ilmenite of middle entrance stove is at least 550 DEG C), and melted in the presence of go back original reagent, thus shape
Into the liquid pig iron and oxidation Titanium slag.
US 8088195B2 are disclosed for containing titanium oxide from the material manufacture including titanium oxide and ferriferous oxide
Slag method.This method is included in heating raw materials mixture in reduction furnace (including titanium oxide, ferriferous oxide and carbon containing
Reducing agent), the ferriferous oxide gone back in original mixture to form the iron of reduction, by the mixture of gained supply to heating melting furnace with
Melt the iron of the reduction and by the iron of the reduction from the slag separation containing titanium oxide, and this is discharged from stove and contain titanyl
The slag of compound.Mixture of raw material caking is set to be imitated to improve the heat transfer in the rotary hearth furnace as reduction furnace and heating melting furnace
Rate.
The content of the invention
The purpose of present disclosure is to provide for preparing the slag containing titanium oxide and life by ilmenite melting
The new method and apparatus of iron.
According to the method for present disclosure, it is characterized in that the method proposed in claim 1.
According to the equipment of present disclosure, it is characterized in that the equipment proposed in claim 23.
According to the slag containing titanium oxide of present disclosure, it is characterized in that proposed in 29 containing titanium oxide
Slag.
According to the pig iron of present disclosure, it is characterized in that the pig iron proposed in claim 30.
According to the method and apparatus of present disclosure at least one of following advantage can be provided relative to prior art：
The electric consumption in the preparation method of the slag containing titanium oxide and the pig iron can be reduced.
The quality of the slag containing titanium oxide can be improved.Or, can be without slag of the infringement containing titanium oxide
More low-quality carbon containing reducer is used in the case of quality.In addition, the amount of reducing agent can be reduced in fusion process.
The amount of carbon in the pig iron can be reduced by using the method according to present disclosure.
Gas formation in the fusion process of the ilmenite of prereduction is less than when the ilmenite using non-prereduction
Gas is formed.Less gas handling system is set up in this permission in electric arc furnaces.
If having preheated supply to the ilmenite of the prereduction of electric arc furnaces, it can further reduce energy expenditure and can carry
The capacity of high electric arc furnaces.
Accompanying drawing is briefly described
Including accompanying drawing to provide a further understanding of the present invention, and accompanying drawing constitutes a part for this specification, explanation
Embodiment of the present invention, and contribute to together with the description to explain the principle of the present invention.In the accompanying drawings：
Fig. 1 is the flow chart explanation according to the method for present disclosure.
Fig. 2 is the diagram of the equipment according to present disclosure.
It is described in detail
On the one hand, the method for preparing the slag containing titanium oxide and the pig iron by ilmenite is disclosed.This method
Comprise the following steps：In prereduction reactor in the presence of a reducing agent prereduction ilmenite so that at least portion in ilmenite
Divide ferrous metal；With the ilmenite of the melting prereduction in electric arc furnaces so that titanium oxide is separated into melted gangue phase and by the pig iron
It is separated into molten metal phase.Titanium optionally from prereduction can be included after pre-reduction procedure according to the method for present disclosure
Iron ore removes the additional step of unreacted reducing agent and gangue.
Or, this method comprises the following steps：A) prereduction in the presence of carbon containing reducer in prereduction reactor
Ilmenite is so that at least part ferrous metal in ilmenite；B) optionally removed from the ilmenite of prereduction unreacted carbon containing
Reducing agent and gangue；And c) in electric arc furnaces melting prereduction ilmenite with by titanium oxide be separated into melted gangue phase and will
The pig iron is separated into molten metal phase.
Slag containing titanium oxide mainly contains titanium oxide.This paper titanium oxide mean in ilmenite or containing
There is the titanium oxide of form of ownership present in the slag of titanium oxide.Most of titanium oxides are TiO2, but for example can also deposit
In Ti2O3, but the ratio of other titanium oxides is less than TiO2Ratio.Slag contains in several percentage ranges in addition
Unreduced ferriferous oxide (mainly FeO).The presence of ferriferous oxide is important to the mobility of slag.Although from purity
Angle can need iron oxide, but in fusion process typically not reduce iron completely and by remaining oxide
It is separated into slag.In one embodiment, the slag containing titanium oxide contains less than 12 weight %, preferably smaller than 10 weights
Measure %, more preferably from about 7 weight % ferriferous oxide.
Slag containing titanium oxide contains various impurity in addition, and its amount depends on raw material and reducing agent property and taken
Certainly in method and step.Typical impurity is aluminium, magnesium, silicon, chromium and sulphur, and it exists with about 1-2 weight % or smaller amount.
Although in the presence of the other elements of some carbon and trace, the pig iron mainly contains metallicity iron.In an embodiment party
In case, the pig iron contains the carbon less than 1 weight %, preferably smaller than 0.8 weight %, more preferably less than 0.6 weight %, more preferably less than
0.4 weight % carbon.
This paper ilmenite mean for prepare the slag containing titanium oxide and the pig iron containing titanium oxide and contain
The mineral feed material of ferriferous oxide.Can be by any mode (such as flotation is selected) known in the art come selected ilmenite.
In the case where the gangue content of raw material is sufficiently low, it is not necessary to selected and unprocessed ilmenite therefore can be used.Ferrotianium
Ore deposit can the titanium oxide containing e.g., from about 45 weight %, 55 weight % or 60 weight %.In addition, ilmenite can contain e.g., from about 30
Weight %, 35 weight % or 38 weight % ferriferous oxide.
In the step a) of this method, prereduction ilmenite.In this step, by a part of ferriferous oxide in ilmenite
It is reduced to metallicity iron.In one embodiment, the reducing agent in step a) be carbon containing reducer, for example anthracite, coke,
Coal, charcoal, charcoal, contain the gas of carbon monoxide or its combination.It is used for using carbon containing reducer according to formula FeO+C → Fe+CO's
Reaction.Different carbon containing reducers is in their reactivity, purity, construction and changes in price, its be when selection be used in
All parameters that technical staff is contemplated that during the Suitable reducing agent of given application.Anthracite, coke, coal, charcoal, wood for example can be used
Charcoal, containing the gas of carbon monoxide or its combination it is used as carbon containing reducer.In one embodiment, using anthracite, Jiao
Charcoal, coal, containing the gas of carbon monoxide or its combination it is used as the carbon containing reducer in step a).The crystallite dimension of reducing agent is excellent
Elect 0.5-20mm as.This size range optimization percent reduction in the case where no reducing agent excessive loss enters gas phase.
In one embodiment, the reducing agent in step a) be the gas containing molecular hydrogen, containing the gas of hydrocarbon or its
Combination.Gas containing hydrocarbon can be such as natural gas.In one embodiment, using carbon containing reducer and it is another type of also
The combination of former agent.For example, the combination of molecular hydrogen and CO gas can be used.
Prereduction can occur in rotary kiln or in a fluidized bed reactor.It is typically for these methods and uses fossil
The heating that fuel is used for needed for technique.In one embodiment, in using rotary kiln or fluidized-bed reactor as step a)
Prereduction reactor.Ilmenite can be introduced into prereduction reactor with (such as group, block or tuberculosis) in the form of luming.May be used also
By ilmenite to be introduced into the form of not luming in prereduction reactor.
Typically, prereduction occurs in reducing atmosphere.The metallicity iron of heat is very easy to reoxidize for ferriferous oxide, and
And this needs to be avoided by protective atmosphere such as nitrogen or argon.If in addition, being for example used as carbon containing reduction using carbon monoxide
Agent, then security reason need strictly contain the reducing agent gas.
In current method, the degree of metallization of iron is at least 50% after prereduction.This paper degree of metallization
Mean total iron ratio in metallicity form in ilmenite.In other words, with (FeMetal/FeAlways) × 100% calculates metallization journey
Degree.It is preferred that the degree of metallization after prereduction is, for example, 70% or 80%.It can reach up to 90% and higher (such as 93%)
Degree of metallization.However, because slag and the pig iron containing titanium oxide are heated in electric arc furnaces to be used to separate, using
The reduction that melting step is used to complete ferriferous oxide in ilmenite can be favourable.
In one embodiment, at least 50 weight %, preferably at least 70 weight %, more of ilmenite are made in step a)
Preferably at least 85 weight % ferrous metal.
As secondary technique, also occurs titanium from TiO2To Ti2O3Reduction.Carrying out this reaction can in some cases limit and carry
The possibility of the degree of metallization of high ferro.
In the step b) of this method, unreacted carbon and gangue are removed from the ilmenite of prereduction.This step is optional
, and the method according to present disclosure therefore can be carried out in the case of without carbon and gangue is removed.The degree example of removal
Such as the gangue content depending on the ilmenite used in the method.Impurity of the carbon containing reducer typically containing at least trace
(it is also removed at least partially in this step).This can allow to prepare purer slag and/or the pig iron containing titanium oxide.
Accordingly, it is possible to which the carbon containing reducer compared with low-purity can be used in prereduction without the unfavorable shadow of the purity to final product
Ring.
In one embodiment, in the step b) using Magnetic Isolation to remove unreacted reducing agent and gangue.
In one embodiment, using Magnetic Isolation to remove unreacted carbon containing reducer and gangue in the step b).In order that magnetic
Property separation be feasible, the ilmenite of prereduction needs to cool down or cooled is less than its Curie temperature.In the case, 700
DEG C and following temperature under Magnetic Isolation be feasible.
In one embodiment, unreacted reducing agent and gangue are removed under 700 DEG C or lower temperature.At one
In embodiment, unreacted carbon containing reducer and gangue are removed under 700 DEG C or lower temperature.When having used except magnetic point
During the other method of the density of the ilmenite based on such as prereduction from beyond or crystallite dimension, holding prereduction that can be favourable
Ilmenite temperature higher than 700 DEG C to reduce the energy expenditure in the step c) of this method.Therefore, in some embodiments
In, the step b) of this method can be carried out at a temperature of more than 700 DEG C.For example, step b) temperature can be 800-1000 DEG C.
The ilmenite of prereduction (either actively or passively) is cooled down after step a) if necessary, then can be in step c)
Reheated before.This can improve the output of melting and further reduce its energy expenditure.Can be at least in part using next
From this method (such as from step a) or c)) recycling heat carry out this preheating.In one embodiment, in step
C) ilmenite of prereduction is preheated before.Reducing agent can be preheated to such as 600 DEG C.
For the efficiency of improved method, unreacted carbon containing reducer can be circulated back to prereduction system.So, it can change
Enter the heat contained in reducing agent and the service efficiency of material.In one embodiment, by the ilmenite separation from prereduction
Unreacted carbon containing reducer be circulated back to prereduction reactor.
In one embodiment, will to be recycled to prereduction from the unreacted reducing agent of the ilmenite of prereduction separation anti-
Answer device and/or electric arc furnaces.Reducing agent can be recycled to electric arc furnaces.Reducing agent can be carbon containing reducer.The separation of reducing agent is simultaneously followed
Ring to electric arc furnaces allows the amount for adjusting the reducing agent brought into melting step.Because unreacted reducing agent can be recycled to pre- go back
Former reactor, is additionally or alternatively recycled to electric arc furnaces by reducing agent, so can be adjusted by the way of this method is best suitable for
The material stream of unreacted reducing agent.In other words, supply to the ratio of the unreacted reducing agent of prereduction reactor can be 0
And change between 100%.Supply to the ratio of the unreacted reducing agent of electric arc furnaces and can change between 0 and 100%.Can be from this
Method removes unreacted reducing agent and gangue (it is recycled to prereduction reactor or electric arc furnaces alternatively or in addition).
In addition, can separate unreacted reducing agent to adjust prereduction by the ilmenite of the prereduction from only a part
Ratio between ilmenite and reducing agent.In other words, the prereduction of unreacted reducing agent and gangue will can therefrom be eliminated
Ilmenite and unsegregated prereduction the supply of both ilmenites to electric arc furnaces, i.e. this method step c).Can also be by not
The ilmenite of processing is added in electric arc furnaces 2.Therefore, the unreacted reducing agent through circulation can be used to realize for melting
Appropriate FeO contents.Depending on method details, it can be heated or cooled and be circulated to prereduction reactor and/or electric arc furnaces not
The reducing agent of reaction.
In the step c) of this method, the ilmenite of melting prereduction in electric arc furnaces.In this step, respectively by titanyl
Compound and metallicity iron are separated into melted gangue phase and metal phase.It is emphasized that this step, which can contain, is present in prereduction
The further reduction of ferriferous oxide in ilmenite.However, this not necessarily and be contemplated that such embodiment, wherein
Using only slags of the step c) with separating metallic iron and containing titanium oxide.
The metal of bottom substantially only contains metallicity iron so that ferriferous oxide is retained in slag.Therefore, slag phase
Ferriferous oxide content depends on the degree of metallization for the iron being present in ilmenite.This can pass through the carbon containing reduction in method of smelting
The amount of agent is adjusted.In order to reduce the ferriferous oxide content of slag, ferrotianium of the reducing agent relative to supply to electric arc furnaces is improved
The amount of ore deposit.More ferriferous oxides are reduced into metallicity iron and molten metal phase is therefore separated into.In an embodiment
In, add reducing agent in the electric arc furnaces in step c).In one embodiment, add and contain in the electric arc furnaces in step c)
Carbonaceous reducing agent.
In the opposite case, less carbon containing reducer will be fed relative to the ilmenite of prereduction and introduces electric arc furnaces
In.If the mobility reduction of such as slag, this can be necessary.Sometimes any carbon containing reducer can not be added to electricity
In arc stove.This can be related alternative solution, if especially model of the degree of metallization of the ilmenite of prereduction in 80-90%
In enclosing.In one embodiment, without addition reducing agent in the electric arc furnaces in step c).In one embodiment, exist
Without addition carbon containing reducer in electric arc furnaces in step c).In other words, in the case of in the absence of the reducing agent added
Carry out melting.
If being not carried out enough slag ferriferous oxide concentration in this way, it can use not by the undressed of prereduction
Ilmenite supplement prereduction ilmenite.In one embodiment, add unprocessed in the electric arc furnaces in step c)
Ilmenite or the ilmenite without prereduction.If will for example omit the ilmenite for separating prereduction and unreacted carbon containing reduction
The method and step b) of agent, and the ilmenite of prereduction contains a large amount of reducing agents, then the unprocessed ilmenite of addition can be used to make
For alternative solution.
Typically, ilmenite is lumpd to improve its particle size before electric arc furnaces is loaded.If most titanium
Iron ores particle can be blown away before being incorporated in melted gangue, then need to complete this process.But after prereduction, can not have
It is necessary to lump ilmenite.This is by the higher proportion institute of the ilmenite of prereduction compared with the ilmenite of non-prereduction
Cause.In one embodiment, the ilmenite of the prereduction used in step c) does not lump.
In one embodiment, step c) is carried out in direct current electric arc furnace.
Direct current electric arc furnace (DC stoves) is different from ac arc furnace (AC stoves) in terms of its structure and using parameter.For example, can
Thinner material is supplied into DC stoves.It provides the more flexible adjustment possibility for adjusting slag basicity.In addition, in DC
The surface reduction of oxide is more efficiently in stove.This is caused by than the higher surface temperature of melted material in AC stoves.This
Outside, volatile component is easier to be transferred in gas phase in DC stoves.In DC stoves electrode consumption reduce because with AC stoves
Three electrodes are compared, an electrode of existence anduniquess.Typically, investment of the investment again smaller than AC stoves for DC stoves.
In one embodiment, the temperature of melted gangue phase is 1450-1850 DEG C, preferably 1550- in direct current electric arc furnace
1750 DEG C, more preferably 1680-1720 DEG C, most preferably from about 1700 DEG C；And the temperature of molten metal phase is than the temperature of melted gangue phase
Spend it is low 40-200 DEG C, preferably 80-150 DEG C.
In one embodiment, step c) is carried out in ac arc furnace.
In one embodiment, the fusion temperature in ac arc furnace be 1450-1850 DEG C, preferably 1530-1750 DEG C,
More preferably 1570-1700 DEG C, most preferably 1650-1680 DEG C.
In prereduction after ilmenite, as long as the ilmenite of prereduction keeps heat, the iron of metallization is just very easy to
Reoxidize.Therefore, it has to protected from the oxygen in oxidation material such as air.The ilmenite of prereduction may be cooled down and incited somebody to action
It is stored in such as bucket, bag or silo (silo).Storage can be airtight and optionally comprising protective gas.At one
In embodiment, after step a), or optionally after step b), the storage prereduction before supply is into step c)
Ilmenite.
However, storing step can be omitted.If preserved under protective gas (such as nitrogen or argon), it will directly can go back in advance
Former ilmenite leads to electric arc furnaces.This method, which can contain, separates unreacted reducing agent (step b)), or can be directly in prereduction
Melting (step c)) (not having step b) therebetween) occurs after step (step a)).
Directly feeding for this paper means a kind of technique, without by the ilmenite of prereduction with intermediate storage thing store or
The storage container being moved to outside technological process.If storage vessel combined with the technique, the ilmenite of prereduction is kept
It is possible in chest or other storage vessels.The combination can be the form of conveyer belt, feed pipe etc..Even if by prereduction
Ilmenite is directly fed to step c) from step a) or step b), can be necessary the ilmenite pond (pool) of prereduction being maintained at
With the speed difference between adjusting process step in the technique.In one embodiment, by the ilmenite of prereduction from step
A) or optionally it is directly fed to step c) from step b).
In being reduced by the iron of carbon containing reducer, carbon monoxide is formd.It can be reacted with aerial oxygen with explosive manner,
And therefore need to protect the processing step for wherein forming carbon monoxide.In one embodiment, step c) electric arc furnaces
Gas atmosphere and step a) and/or step b) gas atmosphere are to separate.In some embodiments, if wherein carried out
Step b), then step a) gas atmosphere and step b) gas atmosphere are to separate.Step a), b) and c) gas composition and
Pressure is separate adjustable.In step c), pressure is remained less than into environmental pressure to avoid from electric arc furnaces gas leakage.
Air seal can cause separating in different process step gas atmosphere.It is known in the art many types
Air seal and select suitable be arranged in the cognition of technical staff.
Electric arc furnaces is can configure to run in batches or continuously.Configuration means to feed (in advance with discontinuous step in batches
The ilmenite of reduction and optional reducing agent and/or unprocessed ilmenite) operation that leads in electric arc furnaces.If technique is to connect
Continuous, then feed material is essentially continuously led in electric arc furnaces.Even continuous technique can also have by for example measuring, supervising
Interruption caused by surveying or safeguarding.This paper semi-continuous technique means a kind of technique, wherein occurring during duration
Charging, but there is the intentional interruption of potential variable-length.In all these Method types, the monitoring of slag and metal depth
It is possible, and can be also sampled to determine product characteristicses.
Implement described above continuous in the case of can directly or therebetween using optional step b) after step a)
, semi-continuous or charging in batches.In one embodiment, continuously or semi-continuously from step a) or optionally from step
Suddenly b) ilmenite of prereduction is supplied to step c).
It is slag and the pig iron containing titanium oxide according to the product of the method for present disclosure.On the one hand, disclose
Slag containing titanium oxide.It is characterized in that it is prepared by the method according to present disclosure.Especially, this contains titanyl
The slag of compound removes TiO2Outside can contain Ti2O3.Slag containing titanium oxide can also contain Ti3O5.Different titanium oxides
Compound shows two kinds of oxidation state of titanium, i.e. Ti4+And Ti3+.Their ratio depends on the FeO of method details especially slag
Content and change.
On the one hand, the pig iron is disclosed.It is characterized in that it is prepared by the method according to present disclosure.Especially,
It is prepared for the pig iron of low carbon content.The carbon content of the pig iron prepared by the method according to present disclosure can contain for example small
Carbon, preferably smaller than 0.8 weight %, more preferably less than 0.6 weight %, more preferably less than 0.4 weight % carbon in 1 weight %.
The pig iron containing such as 0.25 weight % carbon can be prepared.
On the other hand, disclose and contain titanium oxide for being prepared by the method according to present disclosure by ilmenite
Slag and the pig iron equipment.The equipment is included：
- prereduction reactor, for prereduction ilmenite；
- optional separating station, for removing unreacted carbon and gangue from the ilmenite of prereduction；With
- electric arc furnaces, for titanium oxide to be separated into melted gangue phase and the pig iron is separated into molten metal phase.The equipment
It is characterised by
- prereduction reactor is operably connected to separating station and/or electric arc furnaces, for by the ilmenite of prereduction transmit to
Separating station and/or electric arc furnaces；
- optional separating station is operably connected to the ilmenite that prereduction station is used to receive prereduction, and is operatively connected
It is used to transmit the ilmenite for the prereduction for therefrom having eliminated unreacted carbon and gangue to electric arc furnaces to electric arc furnaces；With
Be connected to prereduction reactor and/or separating station is used for reception and therefrom optionally eliminates not-furnace operation
The ilmenite of the prereduction of the carbon and gangue of reaction.
Can use between methods known in the art tissue prereduction reactor and optional separating station, prereduction reactor
Operation connection between electric arc furnaces and between optional separating station and electric arc furnaces.Each operation connection can be separate
, for example, conveyer belt or pipe.Operate connection to include storage box or silo, next method and step is moved to for adjusting
Material ratios.What operation connection can control for computer.
The operation connection that the equipment can be included between separating station and prereduction reactor, for by unreacted reducing agent
Prereduction reactor is recycled to from separating station.The operation connection that the equipment can be included between separating station and electric arc furnaces, for inciting somebody to action
Unreacted reducing agent is recycled to electric arc furnaces from separating station.The equipment can include the operation connection guided into from separating station outside technique
For guiding unreacted reducing agent to leave the technique.Operation for transporting unreacted reducing agent is connected can be comprising storage dress
Put.The operation connection for guiding prereduction reactor and electric arc furnaces into from separating station can have shared storage device.
Operation connection can include the device for being used for that the material transported in equipment to be heated or cooled.Therefore, according to the disclosure
The equipment of content can also include the device for being used for that separated unreacted reducing agent and gangue to be heated or cooled.According to the disclosure
The equipment of content, which can be included also, is used for the device of the ilmenite of heating prereduction before supply is into electric arc furnaces.The equipment can be also
Include the device for heating unprocessed ilmenite before supply to prereduction reactor.
In one embodiment, contained according to the equipment of present disclosure for being continuously or semi-continuously electric arc furnaces
Supply the device of the ilmenite of prereduction.
In one embodiment, the gas atmosphere of the gas atmosphere of electric arc furnaces and prereduction station and/or separating station is point
Open.
In one embodiment, prereduction reactor is rotary kiln or fluidized-bed reactor.
In one embodiment, electric arc furnaces is ac arc furnace.
In one embodiment, electric arc furnaces is direct current electric arc furnace.
The embodiment of the present invention that mutually can be described above in any combination.Can be by several embodiment groups
It is combined to form other embodiments of the present invention.Method, material or device related to the present invention can be included in above
At least one embodiment of the invention of description.
Embodiment
With detailed reference to embodiment of the present invention, the embodiment of the embodiment is illustrated in the accompanying drawings.
Fig. 1 illustrates the method according to an embodiment, and it is used to prepare containing titanyl by ilmenite melting
The slag and the pig iron of thing.This exemplary starts from prereduction reactor prereduction titanium in the presence of a reducing agent
Iron ore, so that at least part ferrous metal (step a)) in ilmenite.Present disclosure is not limited to it is any specific
In the case of theory, in this step, the carbon of reducing agent and the ferriferous oxide being present in ilmenite react to produce metal
Property iron and carbon monoxide.The generation step a) in prereduction reactor.
In the step b) of this method, unreacted carbon and gangue are removed from the ilmenite of prereduction.This step is optional
, and if the step is necessary, then evaluated in each application in the cognition of technical staff.
In the step c) of this method, the ilmenite of melting prereduction by titanium oxide to be separated into melting in electric arc furnaces
Slag phase and the pig iron is separated into molten metal phase.As it is known in the art, discriminably removing each phase from electric arc furnaces.Cause
This this method prepares the slag containing titanium oxide on the one hand, and prepares the pig iron on the other hand.
Fig. 2 is the diagram for being used to prepare the equipment of the slag containing titanium oxide and the pig iron according to present disclosure.It is black
Color arrow shows the direction of technological process and square frame shows device present in equipment.With dotted outline describe optional device and
Method and step.For prepared by ilmenite the equipment 3 of the slag containing titanium oxide and the pig iron comprising for example with process-monitor and
Safety-related a large amount of CONSTRUCTED SPECIFICATIONs.For the sake of clarity, all these devices are eliminated in figure.
In the embodiment of fig. 2, equipment 3 includes prereduction reactor 1 first.Typically from storage device 6 by material
It is anti-that component (i.e. ilmenite concentrate and/or unprocessed ilmenite, reducing agent and other possible additives) leads to prereduction
Answer in device 1.In this embodiment, there are three storage devices 6, therefrom can supply material into technique.Each storage
Device 6 can be used for the mixture of a kind of material component or the material component for two or more.Storage device 6 is measured certainly
In process detail.Such as two or four storage device 6, which may be present, to be used to supply material into prereduction reactor 1.Storage
Reducing agent in device 6 can be carbon containing reducer (such as coke) or other kinds of reducing agent (such as molecular hydrogen).
Adjusted or in the loading process of prereduction reactor 1 in storage device 6 or before storage device 6
Adjustment be introduced into ilmenite concentrate and/or unprocessed ilmenite in prereduction reactor 1, reducing agent and it is possible other
The ratio of additive.Storage device 6 is typically case or silo, and it, which has, is used to control further to transport being released into technique
The instrument for the quantity of material put.Mixing arrangement (not shown) also may be present, for preparing to be fed to the material in prereduction reactor 1
Expect component.Can computer control material release.The material release of settable computer control is surveyed later in response in technique
The technological parameter of amount.Therefore, being included according to the equipment 3 of present disclosure is used to receive at least one technological parameter signal and adjusts
Material discharges to respond the device of this signal.For example, the prereduction degree of the ilmenite of measurable prereduction, and this can be used
Information adjusts the amount of different materials component of the supply into prereduction reactor 1.Optionally, in prereduction reactor 1
Still the ratio of material is can adjust in process.Prereduction reactor 1 is, for example, rotary kiln.
Prereduction is carried out in prereduction reactor 1 (according to the step a) of the method for present disclosure).After this, will
The ilmenite of prereduction is transported to the separating station 4 of the optional step b) for carrying out the method according to present disclosure, or fortune
Transport to the electric arc furnaces 2 for carrying out the step c) according to the method for present disclosure.By operating connection 5 to transport.Optionally
, there is storage device 6 between prereduction station 1 and separating station 4 and/or between prereduction reactor 1 and electric arc furnaces 2 in ground.Make
With storage device 6 with the ratio for the ilmenite for adjusting the prereduction for entering ensuing processing step.As above, storage device 6 can
For case or silo and can computer control them.Can at storage device 6 or elsewhere will be other along operation connection 5
Material component is added to the ilmenite of prereduction to be adjusted into the composition of the ilmenite of step b) or step c) prereduction.Example
Such as, unprocessed ilmenite or carbon containing reducer can be added before step c).
If the method comprising the steps of b), then by operating connection 5 therefrom to eliminate unreacted reducing agent and gangue
The ilmenite of prereduction transported from separating station 4 to electric arc furnaces 2.This same operation connection (it is, for example, conveyer) can include storage
Cryopreservation device 6.Unreacted reducing agent can be recycled back into prereduction reactor 1, for further utilizing (by technique arrow
It is dashed to show this alternative solution optionally).Likely the recycling includes purifying step to remove gangue.In order to
For the sake of clear, the instrument for carrying out such step is eliminated in figure.
Unreacted reducing agent can be recycled to the reducing agent for being used to be used as in melting in electric arc furnaces 2 (technique arrow is empty
Line is to show this alternative solution optionally).Likely the circulation includes purifying step to remove gangue.Risen in order to clear
See, the instrument for carrying out such step is eliminated in figure.If unreacted reducing agent especially is recycled into electric arc furnaces 2,
It can then reduce the need for other reducing agent is added in fusion process.The other reducing agent of addition is likely omitted completely
Need.In order to adjust the technological parameter in fusion process, reducing agent through circulation and in addition can be alternatively added in electric arc furnaces 2
Reducing agent such as anthracite.
Air seal 7 is indicated along the operation connection 5 in the equipment 3 according to present disclosure.Air seal 7 is used for that
This separates the gas atmosphere of single processing step.Although an air seal 7 is only presented for each operation connection 5, it
Quantity and position alterable.In fig. 2, they are positioned at before each ensuing processing step, but can be according to setting
Standby 3 design details carrys out adjustment position.In addition, can have just after previous process steps and ensuing processing step it
Preceding air seal 7.In the case, can independently of processing step gas atmosphere and in transport material and/or prereduction
Gas atmosphere is adjusted during ilmenite.
The ilmenite of prereduction is transported to electric arc furnaces 2 from prereduction station 1 or from separating station 4.Operation connection 5 is (along its hair
Raw transport) it is optionally provided with one or more storage devices 6.In fig. 2, electric arc furnaces 2 is depicted as with melted gangue phase (water
Pingyin shadow) and metal phase (diagonal line hatches).The horizon bar being separately employed on the left side and right side of electric arc furnaces 2 shows slag phase and gold
The position of coming out of the stove of symbolic animal of the birth year.The type of electric arc furnaces 2 is not provided in fig. 2.It can be such as DC stoves, and electric arc furnaces 2 will in this case
Typically there is an electrode.
The ilmenite (using optional additive) of the melting prereduction in electric arc furnaces, separates and collects containing titanium oxide
Slag and the pig iron.For the sake of clarity, electrode and circuit, gas vent and entrance, cooling device, Drechsel system are eliminated
And the every other design details of electric arc furnaces 2, because their design is obvious for technicians.Together
What sample eliminated the slag containing titanium oxide of solidification in electric arc furnaces 2 and/or metal phase freezes lining (freeze
lining).This freezes the refractory liner of lining " isolation " melted gangue and electric arc furnaces, therefore protects the refractory liner from melting
The corrosion impact of slag.Freeze lining presence can the durability to electric arc furnaces refractory liner and the purity to final product all
It is beneficial.
Some embodiments of the present invention are The following description disclosed, such details, which is disclosed, enables those skilled in the art
The present invention is enough utilized based on present disclosure.All steps of embodiment are not discussed in detail, because based on this specification
Many steps will be apparent for those skilled in the art.
Embodiment 1
Prereduction contains 48 weight % TiO in a fluidized bed reactor2The ferriferous oxide of equivalent and 48 weight %
(FeO and Fe2O3) (batch 1) or 54 weight % TiO2The ilmenite of equivalent and 40 weight % ferriferous oxide (batch 2).
Prereduction is carried out at a temperature of about 950 DEG C and in the gaseous environment of closing.Carbon containing reducer is used as using coke.The work
Skill typically produces 75-85% ferrous metal degree, but it is accessible to be up to 95% degree of metallization.Prereduction
The degree of metallization of ilmenite change between 14% and 58%.
By analyzing total Ti contents of sample and as only existed TiO2To provide its amount so as to calculate TiO2Equivalent
(TiO2 ekv).In other words, the Ti containing variable proportion can be provided in suitable mode4+And Ti3+Sample Ti contents.
In the case, the ilmenite of prereduction is stored in single silo and is filled to by vibrating feeder (conveyer)
Electric arc furnaces.However, in an alternative solution, the ilmenite of prereduction is supplied to electric arc furnaces by specifically feeding silo
In.Or, directly feeding for the expansion for passing through feed pipe can be used.In these cases, arrange using timing dual-seal
Gas atmosphere and the atmosphere of previous steps of electric arc furnaces is kept to separate.
Unreacted coke is separated from the ilmenite of prereduction by Magnetic Isolation before melting.Or, base can be used
In density or method based on crystallite dimension.The coke of recovery is recycled back into prereduction technique.At 700 DEG C or less
At a temperature of occur Magnetic Isolation.
Carry out the ilmenite of melting prereduction using the coke of crushing as carbon containing reducer in ac arc furnace.As right
Than using unprocessed ilmenite.Added based on the FeO contents of the slag containing titanium oxide determined in fusion process
Coke.Added to electric arc furnaces coke amount every 100kg prereduction ilmenite 1.5 and 6.7kg between change.It can be used
Coke with various grain sizes, and select suitable crystallite dimension to depend on electric arc furnaces, feed composition and other techniques
Parameter, and can be determined by technical staff.Smelting temperature changes between 1530-1579 DEG C and 1650-1680 DEG C.Using higher
Temperature range, realize higher iron reduced level.
The slag containing titanium oxide of gained contains 58.3-75.4 weight % TiO2 ekvWith 5-10 weight % FeO.
In addition, the slag contains 1.6-2.7 weight % SiO2, 2.5-3.3 weight % Al2O3, 0.07-0.09 weight % carbon,
0.02-0.05 weight % sulphur and 0.4-1.9 weight % CaO.
The pig iron of gained contains 0.54-0.98 weight % carbon.Sulphur, titanium, the concentration of manganese and phosphorus keep low and part
Less than detectable limit.
Contrasted with unreduced ilmenite, reduce the power consumption of melting.Calculated for the ilmenite of prereduction
Power consumption change between 610-1075kWh/t slags.In the case of no prereduction, corresponding value will be 808-
1529kWh/t slags.Therefore, the energy expenditure of calculating is reduced by about 25-30%.
Embodiment 2
Use the TiO containing 59.8 weight %2With 34.8 weight % ferriferous oxide (FeO and Fe2O3) ilmenite be used for
Prepare the ilmenite of prereduction at a temperature of 1100-1150 DEG C as carbon containing reducer using coal in rotary kiln.Then exist
The ilmenite of melting prereduction is used to prepare slag and the pig iron containing titanium oxide in direct current electric arc furnace.
The ilmenite of the prereduction of two batches is used in an experiment, and one with 85.7% degree of metallization, (A is criticized
It is secondary), and another has 58.2% degree of metallization (B batches).Using A batches and unprocessed ilmenite as 50%/
50% mixture is supplied to electric arc furnaces, is equivalently, however supplied B batches to electric arc furnaces.Result is unprocessed with being used only
The process ration of ilmenite.The ilmenite of prereduction is stored in bucket and electric arc furnaces is filled to by vibrating feeder (conveyer).So
And, directly feed (it is arranged equipped with timing dual-seal) by the expansion of silo or feed pipe is alternative solution.
Carry out the ilmenite of melting prereduction using anthracite as carbon containing reducer in direct current electric arc furnace.The amount of reducing agent
Change, and be 3.5 weight % or 5.7 weight % (i.e. 96.5 weight % or 94.6 weight the % ilmenite and 3.5 of combined feed
Weight % or 5.7 weight % anthracite).Added to electric arc furnaces anthracitic amount therefore for per 100kg ilmenite 3.7 or
5.7kg。
Ratio between adjustment electric arc furnaces power and rate of feed causes slag temperature to maintain about 1680-1700 DEG C, and it takes
Certainly in slag FeO contents.Sum it up, temperature changes between 1630-1730 DEG C.1690-1720 DEG C of slag temperature to containing
The slag for having titanium oxide provides 7-8 weight % FeO.Purpose is that slag flow is maintained at into sufficiently high level.With this
Meanwhile, form the so-called of solid slag along electric arc furnace wall and freeze lining.This prevents electric arc furnace lining to be dissolved to slag of coming out of the stove
In.Molten metal temperature is about 1560-1580 DEG C.For example, molten metal temperature is 1550 DEG C.
Electric arc furnaces is operated using the slight underpressure (0.1 millibar) produced by pumping blower fan.Burning arc in a combustion chamber
The ignitable components of furnace gases.
When the ilmenite of melting B batches, and during by being added to electric arc furnaces relative to 3.4% carbon of ilmenite weight, institute
The slag containing titanium oxide obtained contains 8.5-9.7 weight % FeO.When carbon rate of feed is improved to 3.7 weight %, prepare
Slag containing 5.4-6 weight %FeO.In experimentation, the FeO contents of slag change simultaneously between 3 and 12 weight %
And typically 5 to 10 weight %.The amount of carbon is calculated as the carbon (C available for reductionfix).It passes through from supply to the technique
In the quality of carbon containing reducer ash, volatile matter, sulphur and the phosphorus content (weight %) of carbon containing reducer is subtracted to calculate.
Most of slags contain titanium oxide (with TiO2And Ti2O3Form).The TiO of slag2Content is in 76.9 weight %
And 88.4 change between weight % (be calculated as TiO2 ekv).Sulphur (average 0.10 weight of slag in addition containing 0.15-0.5 weight %
Measure %), and phosphorus content remains less than 0.05 weight % detectable limit.
The pig iron of gained contains 0.25 weight % carbon, itself and using non-prereduction ilmenite method contrast be very
Low value.Metal contains 0.17-0.3 weight % sulphur, the weight % of average out to 0.20.Phosphorus content 0.07 and 0.4 weight % it
Between scope, the average value with 0.10 weight %.
Contrasted with unreduced ilmenite, as described in table 1, the power consumption of melting reduces.
Table 1：Energy expenditure (kWh/t ilmenites) for stable state smelting technology
* assume 78% the thermal efficiency
* * 50%/50% unprocessed ilmenite and A batches
For the ilmenite of the prereduction of A batches and the mixture of unprocessed ilmenite, commercial scale prediction
The power consumption being computed is thus the 88% of unprocessed ilmenite.When ilmenite (the B batches) using only prereduction, energy
Amount consumption is the 76% of unprocessed ilmenite.
With advances in technology, it will be readily apparent to one skilled in the art that can adopt in various manners to implement
The basic conception of the present invention.Therefore the present invention and its embodiment are not limited to embodiments described above；It is opposite they can be
Change in the range of claim.
Claims (31)
1. the method for preparing the slag containing titanium oxide and the pig iron by ilmenite, it is characterised in that this method includes following
Step：
A) in prereduction reactor (1) in the presence of a reducing agent prereduction ilmenite so that at least part iron in ilmenite
Metallization；
B) unreacted reducing agent and gangue optionally are removed from the ilmenite of prereduction；With
C) in electric arc furnaces (2) ilmenite of melting prereduction so that titanium oxide is separated into melted gangue phase and the pig iron is separated
Into molten metal phase.
2. method according to claim 1, wherein anti-using rotary kiln or fluidized-bed reactor as the prereduction in step a)
Answer device (1).
3. according to the method for claim 1 or 2, the reducing agent in wherein step a) is carbon containing reducer, such as anthracite, Jiao
Charcoal, coal, charcoal, charcoal, contain the gas of carbon monoxide or its combination.
4. according to the method for claim 1 or 2, the reducing agent in wherein step a) is the gas containing molecular hydrogen, contains hydrocarbon
Gas or its combination.
5. according to the method for any one of preceding claims, wherein make at least 50 weight % of ilmenite in step a), it is excellent
Select at least 70 weight %, more preferably at least 85 weight % ferrous metal.
6. according to the method for any one of preceding claims, wherein unreacted to remove using Magnetic Isolation in step b)
Reducing agent and gangue.
7. method according to claim 6, wherein removing unreacted reducing agent and gangue under 700 DEG C or lower temperature.
8. according to the method for any one of preceding claims, wherein making the unreacted reduction from the ilmenite separation of prereduction
Agent is recycled to prereduction reactor (1) and/or electric arc furnaces (2).
9. according to the method for any one of preceding claims, the ilmenite of the prereduction used in wherein step c) is not lump
's.
10. according to the method for any one of preceding claims, wherein preheating the ilmenite of prereduction before step c).
11. according to the method for any one of preceding claims, wherein without addition reduction in electric arc furnaces (2) in step c)
Agent.
12. according to the method for any one of claim 1-10, wherein the middle addition reducing agent of electric arc furnaces (2) in step c).
13. according to the method for any one of preceding claims, wherein the middle addition of electric arc furnaces (2) in step c) is unprocessed
Ilmenite or the ilmenite without prereduction.
14. according to the method for any one of preceding claims, wherein carrying out step c) in direct current electric arc furnace (2).
15. the temperature of melted gangue phase is 1450-1850 in method according to claim 14, the wherein direct current electric arc furnace (2)
DEG C, preferably 1550-1750 DEG C, more preferably 1680-1720 DEG C, most preferably from about 1700 DEG C；And the temperature of molten metal phase is than molten
The temperature of melting slag phase is low 40-200 DEG C, preferably 80-150 DEG C.
16. according to the method for any one of claim 1-13, wherein carrying out step c) in ac arc furnace (2).
17. fusion temperature is 1450-1850 DEG C, preferably in method according to claim 16, the wherein ac arc furnace (2)
1530-1750 DEG C, more preferably 1570-1700 DEG C, most preferably 1650-1680 DEG C.
18. according to the method for any one of preceding claims, wherein from step a) or optionally from step b) continuously or half
Continuously the ilmenite of prereduction is supplied to step c).
19. according to the method for any one of preceding claims, wherein from step a) or optionally from step b) directly by advance
The ilmenite of reduction is supplied to step c).
20. the gas atmosphere of the electric arc furnaces (2) of method according to claim 19, wherein step c) and step a) and/or step
B) gas atmosphere is separated.
21. according to the method for any one of claim 1-18, wherein after step a) or optionally after step b),
The ilmenite of prereduction is stored before supplying into step c).
22. according to the method for any one of preceding claims, wherein the slag containing titanium oxide contain less than 12 weight %,
Preferably smaller than 10 weight %, more preferably from about 7 weight % ferriferous oxide.
23. according to the method for any one of preceding claims, the wherein pig iron contains the carbon less than 1 weight %, preferably smaller than 0.8
Weight %, more preferably less than 0.6 weight %, more preferably less than 0.4 weight % carbon.
24. for by the method for any one according to preceding claims by ilmenite prepare the slag containing titanium oxide and
The equipment (3) of the pig iron, the equipment is included
- prereduction reactor (1), for prereduction ilmenite；
- optional separating station (4), for removing unreacted reducing agent and gangue from the ilmenite of prereduction；With
- electric arc furnaces (2), for titanium oxide to be separated into melted gangue phase and the pig iron is separated into molten metal phase；Feature exists
In
- prereduction reactor (1) is operably connected to separating station (4) and/or electric arc furnaces (2), for by the ilmenite of prereduction
Transmit to separating station (4) and/or electric arc furnaces (2)；
- optional separating station (4) is operably connected to the ilmenite that prereduction station (1) is used to receive prereduction, and operatively connects
Being connected to electric arc furnaces (2) is used to transmit the ilmenite for the prereduction for therefrom eliminating unreacted carbon and gangue to electric arc furnaces (2)；
With
- electric arc furnaces (2) is operably connected to prereduction station (1) and/or separating station (4), is optionally therefrom eliminated for receiving
The ilmenite of the prereduction of unreacted carbon and gangue.
25. equipment (3) according to claim 24, the wherein equipment (3), which are contained, to be used to be continuously or semi-continuously electric arc furnaces
(2) device of the ilmenite of supply prereduction.
26. according to the equipment (3) of claim 24 or 25, wherein the gas atmosphere of electric arc furnaces (2) and prereduction station (1) and/or
The gas atmosphere of separating station (4) is separated.
27. according to the equipment (3) of any one of claim 24-26, wherein prereduction reactor (1) is rotary kiln or fluid bed
Reactor.
28. according to the equipment (3) of any one of claim 24-27, wherein electric arc furnaces (2) is ac arc furnace.
29. according to the equipment (3) of any one of claim 24-27, wherein electric arc furnaces (2) is direct current electric arc furnace.
30. the slag containing titanium oxide, is characterised by it by the method for any one according to claim 1-23 to prepare.
31. the pig iron, is characterised by it by the method for any one according to claim 1-23 to prepare.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20155066 | 2015-01-30 | ||
| FI20155066A FI20155066A (en) | 2015-01-30 | 2015-01-30 | A process for the production of slag and crude iron containing titanium oxide from ilmenite and a plant |
| PCT/FI2016/050053 WO2016120529A1 (en) | 2015-01-30 | 2016-01-28 | Method for producing titanium oxide-containing slag and pig iron from ilmenite and a plant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107208184A true CN107208184A (en) | 2017-09-26 |
Family
ID=55409856
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|---|---|---|---|
| CN201680006936.2A Pending CN107208184A (en) | 2015-01-30 | 2016-01-28 | Method and apparatus for preparing the slag containing titanium oxide and the pig iron by ilmenite |
Country Status (7)
| Country | Link |
|---|---|
| CN (1) | CN107208184A (en) |
| BR (1) | BR112017015641A2 (en) |
| CA (1) | CA2974263A1 (en) |
| EA (1) | EA201791434A1 (en) |
| FI (1) | FI20155066A (en) |
| WO (1) | WO2016120529A1 (en) |
| ZA (1) | ZA201704911B (en) |
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| CN108411126B (en) * | 2018-05-01 | 2023-10-17 | 昆明有色冶金设计研究院股份公司 | Titanium slag smelting system and method based on pre-reduction |
| CN111440908B (en) * | 2020-05-22 | 2021-06-22 | 安徽工业大学 | Method for converting titanium component in titanium-containing blast furnace slag into ilmenite |
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| US3765868A (en) | 1971-07-07 | 1973-10-16 | Nl Industries Inc | Method for the selective recovery of metallic iron and titanium oxide values from ilmenites |
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| JP4153281B2 (en) | 2002-10-08 | 2008-09-24 | 株式会社神戸製鋼所 | Method for producing titanium oxide-containing slag |
| AU2013383015B2 (en) * | 2013-03-18 | 2016-09-08 | Outotec (Finland) Oy | Process and plant for producing titanium slag from ilmenite |
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- 2015-01-30 FI FI20155066A patent/FI20155066A/en not_active Application Discontinuation
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- 2016-01-28 WO PCT/FI2016/050053 patent/WO2016120529A1/en active Application Filing
- 2016-01-28 CA CA2974263A patent/CA2974263A1/en not_active Abandoned
- 2016-01-28 BR BR112017015641A patent/BR112017015641A2/en not_active Application Discontinuation
- 2016-01-28 CN CN201680006936.2A patent/CN107208184A/en active Pending
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2017
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| CN1429919A (en) * | 2002-10-18 | 2003-07-16 | 中国科学院过程工程研究所 | Method of producing titanium enriched material using titanium mineral |
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Also Published As
| Publication number | Publication date |
|---|---|
| EA201791434A1 (en) | 2018-01-31 |
| WO2016120529A1 (en) | 2016-08-04 |
| CA2974263A1 (en) | 2016-08-04 |
| FI20155066A (en) | 2016-07-31 |
| ZA201704911B (en) | 2019-06-26 |
| BR112017015641A2 (en) | 2018-03-13 |
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