CN1037982C - Process for recovery of titanium values from complex matrix comprising titanium nitride - Google Patents
Process for recovery of titanium values from complex matrix comprising titanium nitride Download PDFInfo
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- CN1037982C CN1037982C CN91105786A CN91105786A CN1037982C CN 1037982 C CN1037982 C CN 1037982C CN 91105786 A CN91105786 A CN 91105786A CN 91105786 A CN91105786 A CN 91105786A CN 1037982 C CN1037982 C CN 1037982C
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- titanium
- matrix
- carbon
- nitrogenize
- chlorination
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- 238000000034 method Methods 0.000 title claims abstract description 62
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000010936 titanium Substances 0.000 title claims abstract description 53
- 239000011159 matrix material Substances 0.000 title claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 51
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title description 8
- 238000011084 recovery Methods 0.000 title description 2
- 238000005121 nitriding Methods 0.000 claims abstract description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 38
- 239000007858 starting material Substances 0.000 claims description 38
- 238000005660 chlorination reaction Methods 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 230000014509 gene expression Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 230000011218 segmentation Effects 0.000 claims description 3
- 239000002893 slag Substances 0.000 abstract description 32
- 239000002994 raw material Substances 0.000 abstract description 21
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910001200 Ferrotitanium Inorganic materials 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000460 chlorine Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000003245 coal Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- 229940045605 vanadium Drugs 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910003902 SiCl 4 Inorganic materials 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- -1 perhaps Substances 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000002175 menstrual effect Effects 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
- C01B21/0765—Preparation by carboreductive nitridation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- 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
- C22B34/1218—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 obtaining titanium or titanium compounds from ores or scrap by dry processes
-
- 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
- C22B34/1218—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 obtaining titanium or titanium compounds from ores or scrap by dry processes
- C22B34/1222—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 obtaining titanium or titanium compounds from ores or scrap by dry processes using a halogen containing agent
-
- 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
- C22B34/1236—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 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—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 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/1245—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 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a halogen ion as active agent
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
- Y02P10/20—Recycling
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Abstract
The present invention provides a method for recovering titanium from a compound matrix containing titanium nitride, which comprises the following steps: chlorinating titanium nitride in a matrix in order to obtain a reaction product containing titanium chloride; separating the titanium chloride from the reaction product. The present invention also provides a method for producing the compound matrix containing the titanium nitride by nitriding compound raw material containing titanium. For example, titanium in compound metallurgy ferrotitanium slag, ilmenite, perovskite, geikielite and fassaite is produced by the method.
Description
The present invention relates to reclaim the method for titanium with the form of titanium chloride or titanium oxide by containing with in the complex matrix of titanium nitride as its component.More particularly, the present invention relates to a kind of being applicable to by the method that reclaims titanium in the described matrix with the titanium chloride form, and described matrix is by Nitriding Compound mineral or metallurgical raw material, as ilmenite or contain the ferrotianium slag of titanium oxide and other metal oxides, particularly contain 30-80% (weight) or lower low-grade ferrotianium slag, wherein titanium is with TiO
3The ilmenite of expression and blended metal oxide or titanate makes.
Chinese patent CN1033264A (application number 87107488.5) discloses under 1350-1400 ℃ temperature that reduction contains titanium in the metallurgical slag of titanium dioxide as reductive agent with carbon, make slag carbonization and nitrogenize, afterwards, the carbonization of the complex matrix form of nitrogen titanium and the slag of nitrogenize are carried out chlorination at low temperatures and generated titanium chloride.
The object of the present invention is to provide a kind of by containing titanium nitride as the method that reclaims titanium in the complex matrix of its composition.
The step that aforesaid method comprises is:
Titanium nitride in the chlorination matrix, and obtain containing the reaction product of titanium chloride;
Separate titanium chloride from reaction product, this method comprises the step of producing the titanium nitride matrix, and said step is by the TiO in the contained composite titanium in the nitrogenize starting material
2, and nitriding step is under 1000-1800 ℃ high temperature, contacts under situation about having in the presence of the carbon of the reducing environment of providing, and is having in the presence of the carbon of capacity, consuming existing all oxygen in the environment, and provide in the reducing material with TiO
2The titanium value of expression is the required stoichiometric excessive carbon of titanium, and this method comprises that also carbon mixes with starting material with the form of segmentation and the step of reducing environment is provided, the method is characterized in that after the nitrogenize with chlorination before, the step of separation carbon from matrix.
To explain below, the chlorination of titanium nitride is to obtain titanium chloride by chloridating gas is contacted under 200-500 ℃ temperature with matrix, and as mentioned above, this method comprises by reclaiming titanium in the matrix that obtains by Nitriding Compound mineral or metallurgical raw material.Therefore, present method can comprise, makes the step of nitrogen titanium matrix by the titanium in the nitrogenize titaniferous composite materials.
Carbonaceous fuel burns in air so that combustible gas to be provided, and combustible gas is contacted with starting material so that described high temperature to be provided, and provide reducing environment with the carbon monoxide form, and the chlorination of titanium nitride is by being selected from Cl
2, HCl, CCl
4, SCl
2And composition thereof chloridating gas, under 350-450 ℃ temperature, contact with titanium nitride.Chloridating gas is Cl
2, it forms the Cl of 20-80% (volume) with nitrogen dilution
2Mixed gas.The matrix of nitrogen titanium also contains the metal except that titanium, this method before chlorination by the step of separating the metal except that titanium in the described matrix.
Though present method for as contain the above high titanium value of 80% (weight) (with TiO
2Expression) mineral or metallurgical raw material have actual value, but present method is useful as ilmenite or slag particularly for metallurgical raw material, and they more or less are compound, and have be lower than 80% (weight) or be lower than 30% or even lower low titanium value (with TiO
2Expression).Therefore, starting material can be that a kind of 80% (weight) titanium value that contains at the most is (with TiO
2Expression) compound metallurgical ferrotianium slag, perhaps, starting material also can be selected from rutile, ilmenite, uhligite, picrocrichtonite, pyrgom with and composition thereof mineral.
Because nitriding step is at high temperature, with nitrogen by or cross granular starting material and implement easily, method can comprise a kind of raw-material step of nitrogenize, this raw-material largest particle particle diameter is as best one can little by the mode that can implement or suit, 10-2000 μ m for example, its median size is at most 600 μ m, and preferably, the scope of largest particle particle diameter and average grain diameter is at 50-100 μ m.Therefore present method can comprise, reduced raw material particle size to largest particle particle diameter 2000 μ m at the most before the titanium nitrogenize, and the average grain particle diameter is at most the step of 600 μ m.The reduction of particle diameter, general with crushing and grinding, and the distribution of final grain diameter and grain diameter is decided by the consideration of economic aspect usually.Be easy to high speed and fully carry out nitrogenizing reaction owing to surface-area increases, the cost of grinding can be disregarded.
As mentioned above, nitrogenize generally is under any pressure condition of high temperature, normal pressure or highly compressed, with nitrogen by or cross the particulate state starting material and carry out, and in reducing environment, be effective with excessive nitrogen, and reducing environment can be, for example, by in starting material, provide by suitable proportion composite grain shape carbon.In other words, the nitrogenize of titanium is can be by under high temperature and reducing environment, and the nitrogen that stoichiometry is excessive contacts with starting material and carries out.The good news is, use the excessive nitrogen of stoichiometry, can from reaction zone, remove carbonic acid gas, and can suppress the generation of undesirable titanium carbide.Be used for the preferred gas of nitrogenize, though comprise the nitrogen of at least 25% (volume), certainly, nitrogen content high more (up to 100%) then can be obtained better nitriding result.Nitriding step can be at suitable metallurgical reaction, and as rotary kiln or cupola furnace, fluid bed reactor in the perhaps similar reactor, carries out with solid raw material.Starting material can certainly use liquid, and nitrogenize is in bucket or electric furnace, are undertaken by using suitable jet apparatus injection nitrogen.
Preferably, starting material are with the carbon uniform mixing behind the material mixture of supplying raw materials, and are best under 1200-1350 ℃ of temperature at 1100-1600 ℃, with nitrogen defeated through or failed starting material.The required time of nitrogenize becomes inverse relationship with temperature, and in addition, employed accurate temperature will be considered economy, uses the advantage of lesser temps to disappear because of the long nitridation time of need.As implied above, nitrogen will carry out under the situation that the carbon that the reducing environment of providing is arranged exists under 1000-1800 ℃ temperature with raw-material the contact, exists at the carbon that the amount of being is arranged, consuming existing all oxygen in the environment, and provide in the starting material reduction titanium value (as TiO
2) be the excessive carbon of the needed stoichiometry of titanium.
Certainly, nitrogen is input to the speed of mixture of raw material, should be enough to reach in the allowed time satisfaction of nitrogenize.Average retention time can be 1/2-5 hour, and was perhaps shorter, as 1-3 hour.In addition, at at a high speed defeated nitrogen, the cost of defeated nitrogen and thermal losses and and between the unreacted nitrogen by raw mix, should consider from economic aspect is compromise: and it should be noted that the gas excellent contact, for example, in fluidized-bed or rotary kiln, then enough with the starting material that segment as 1-2 hour shorter residence time.
Nitrogenizing reaction is a strong endothermic reaction.Therefore must provide heat to keep temperature of reaction to reaction zone.This can pass through reactor, for example, heats by using electrical heater or plasma arc, and/or implements by the heating of giving of nitrogen.When nitrogen is pure basically, and during by suitable heat exchanger indirect heating, then wherein any heating can be by the device of burner, and common combusting carbonaceous fuel is as producer gas, coal-tar fuel, heavy oil or meticulous coal, all use air, to obtain required temperature, therefore, with the mixture of nitrogen and carbon monoxide and water vapor, under the condition of anaerobic basically, be passed in the raw mix as nitrogen.In other words, carbonaceous fuel can burn in air and provides combustion gases, this gas to contact with starting material so that described high temperature to be provided, and provides reductive condition required carbon amount with the form of carbon monoxide.Therefore, as implied above, method will comprise that the carbonaceous material with the finely divided particulate shape mixes with starting material so that the step of reducing environment to be provided.
According to other method, except other heat supply method, can make input contain aerobic, air in the raw-material nitrogen material gas, and contain the external carbon of capacity in the starting material, with by burning by removing deoxidation in the air, this is feasible to replace heat supply.This just helps to keep the heat supply of nitrogenizing reaction.
The essentially no oxygen of nitrogen when input mixes the carbon amount ratio that forms raw mix with starting material, can be the 100-300% of stoichiometric number, is generally the 150-200% of stoichiometric number, and ＂ stoichiometric number ＂ is meant and reduces titanium (with TiO in starting material
2Expression) required carbon amount when being TiN, this depends on existing reaction conditions.As mentioned above, when input air, the external carbon of capacity then will be provided, to guarantee from air, removing deoxidation, for example, for this reason, except essential oxide compound being reduced in the nitride process of titanium in the nitrogenize starting material, with institute's bonded oxygen in the starting material react necessary excessive beyond, the excessive carbon amount of stoichiometry slightly also will be arranged.As mentioned below, if chlorination is to carry out in than the reducing environment a little less than the nitrogenize environment, then this method need be removed some excessive carbon at least certainly after nitrogenize.
With starting material blended carbon, mainly be coal, hard coal, coke, industrial carbon, charcoal, graphite or analogue, have been found that, decolorizing carbon, as dim or jet-black, all can obtain satisfied result, same, preferred carbon, should be form and starting material uniform mixing, and the particle diameter of carbon be similar to raw-material particle diameter, for example with segmentation, 50-100 μ m, or littler.These small-particle particle diameters are easy to separate carbon in the nitrogenize material after the nitrogenize from fluidized-bed, take or wash out carbon granule out of by the high speed fluidisation.
Preferred chlorinating step is to carry out in the reducing environment more weak than nitrogenize environment.
Promote than carrying out chlorination in the reducing environment more weak when the nitrogenize, mainly can comprise, carbon is mixed the reducing environment of carrying out nitrogenize to provide with starting material, after its add-on and/or speed should make nitriding step, the ratio of the carbon in the nitrogenize matrix will be lower than when nitrogenize begins and the ratio of raw material blended carbon, and preferably, as far as possible or feasible low as best one can, in nitridation process, making whole carbon all be oxidized to carbonic acid gas basically, is irreducibility with the environment that causes chlorination to be carried out basically.
If require to have quite high carbon ratio example in the starting material, with promote titanium rapidly and/or nitrogenize fully, then when nitrogenize is complete, can not guarantee carbon-free basically.In this case, method will comprise, behind nitriding step, before the chlorinating step, separate the step of carbon from the matrix that contains titanium nitride.This can implement by physical separation step, for example, with gas fluidized when containing the titanium nitride matrix, then can blow away separation carbon, and when containing the titanium nitride matrix with the liquid fluidisation, but flotation separation carbon then, the carbon of flocculated suspension in liquid and contain the titanium nitride matrix, then by as flotation or similar method by wherein separating throw out.In other words, method comprises, after nitrogenize and before the chlorination, separates the step of carbon from matrix.Can in the used fluidized-bed of nitrogenize, separate carbon, to reduce the reductibility of environment by blowing.
Beyond thoughtly be, before chlorinating step, the reductibility of described reduction environment can suppress or be more preferably other metal oxide formation muriate in the elimination starting material in the chlorinating step process, reduce the consumption of chlorine thus, and reduce undesirable muriate product.The applicant thinks that this characteristics of present method help limiting those titaniums, the muriatic formation in the gaseous metal of iron and vanadium, and the formation of the solid chloride of restriction manganese, magnesium and calcium.In the titanium chloride product, the metal chloride except that titanium all is undesirable impurity, and, by fusion, may aggravate reactor, as the obstruction of fluidized-bed in described temperature.
Because in starting material, generally there is (＜1% (weight)) in manganese with admissible a small amount of ratio, and its muriatic fusing point and boiling point be respectively 650 ℃ and 1290 ℃, because it is easy to from TiCl
3The middle separation be not so be considered as TiCl to it
4Undesirable especially impurity in the product.Similarly consideration also is applicable to calcium and magnesium, and their amount is higher, but has high melt point and boiling point.In addition, because the chlorination of magnesium and calcium, the chlorination than titanium on kinetics is slow, thereby gaseous state TiCl
4Can proceed to much bigger degree, and cause the formation of solid chloride of magnesium and calcium quite few, owing to the muriate that consumes magnesium and calcium helps TiCl
4Production, thereby these impurity are being no more than to allow ratio and exist to be necessary.
For example, the chlorination of the titanium nitride that obtains from the nitrogenize starting material can be adopted a kind of chloridating gas, as, HCl, CCl
4, SCl
2Or preferred Cl
2, in suitable temperature (to Cl
2For 200-500 ℃, be 350-450 ℃ preferably) stimulate the menstrual flow or undertaken by the nitrogenize matrix.Change sentence and say that perhaps the chlorination of titanium nitride can be by being selected from Cl
2, HCl, CCl
4, SCl
2With and composition thereof chloridating gas, under 350-450 ℃ temperature, contact with matrix and obtain titanium chloride.Relevant this respect, the applicant is surprised to find that, selects suitable nitriding temperature (as 1200-1350 ℃), can guarantee that after its nitrogenize, starting material still keep being suitable for the graininess of chlorination grain diameter.There is no need further to reduce again raw-material particle diameter, and only need cool off and move into suitable reaction vessel, as fixed bed, reverse swirler or simply, fluidized-bed.After described cooling, by magnetic separate and/or weight fraction from, any metal that can remove in the nitridation process simply to be produced.Thus, can further reduce or be more preferably the generation of removing undesirable metal chloride.
Above-mentioned chlorination temperature will be selected like this, makes that the TiN in the nitrogenize matrix is converted to TiCl
4, and under these temperature, the applicant thinks that other the main volatilizable chlorizate that can give birth to by any thing volume production is a transition metal chloride, as iron(ic) chloride (FeCl
3), vanadium chloride (VCl
4), vanadium oxydichloride (VOCl
3) and silicon chlorides (SiCl
4).Any FeCl
3Or vanadium chloride and/or vanadium oxydichloride and TiCl
4Condensation in the gas that is easy to together produce by photochlorination vessel.Any FeCl that produces
3, can be at normal atmosphere, basically than TiCl
4Or VOCl
3Condensation under the higher temperature, and can be easy to therefrom remove, for example in swirler or similar containers, by isolating solid FeCl at 290 ℃
3And TiCl
4Gas.It should be noted that FeCl in this respect
3306 ℃ of fusions, and be decomposed into FeCl at 315 ℃
2And Cl
2, FeCl
2Fusing point be higher than 315 ℃, and Cl
2Be gas; TiCl
4136 ℃ of vaporizations; VOCl
3126 ℃ of vaporizations; SiCl
458 ℃ of vaporizations, and VCl
4148 ℃ of vaporizations.Therefore, TiCl thereafter
4With any VOCl
3Or VCl
4Condensation together is (as by any SiCl
4Or separate in the analogue), separate after this pure basically TiCl then by known distillating method
4Can be easy to be oxidized to TiO by currently known methods
2, a kind of valuable pigment.
It should be noted that calcium, magnesium and manganese are all arranged at most of oxygen containing composite mineralss.Thereby they also are present in the used most of starting material of present method, particularly in the metallurgical slag.Present method is distinctive to be to adopt the low temperature chlorination temperature with surprising advantages, and this causes reducing the chlorination of these metals.In addition, the more important thing is that these metal chlorides are solid in the time of 200-500 ℃.Compare with the sort of chlorating that under temperature higher and that be enough to these metal chlorides of fusion, carries out that this is that substantial advantage is arranged, because fusion can cause reactor, as the obstruction of rotary kiln or fluidized-bed.
About chlorination, it should be noted that this is a kind of thermopositive reaction.For example, fluidized-bed reactor is used for chlorination, then the heat of Chan Shenging can be removed by fluidizing gas, and majority of gas is an inert carrier gas, and if needed, heat also can reclaim from these gases with currently known methods.
Chloridating gas can as use a kind of rare gas element by the form of dilution, fails the matrix of via nitride as argon gas or nitrogen dilution, when chloridating gas is Cl
2The time, can be by at least 10% Cl
2The mixed nitrogen of (volume), for example, 20-80% (volume) Cl
2, and can under normal pressure or high pressure, import.Therefore, in a concrete scheme, chloridating gas can be the Cl with nitrogen dilution
2, form and contain 20-80% (volume) Cl
2Mixed gas.As what considered economically, chloridating gas can be failed the via nitride matrix, and its average retention time is 10-120 minute, and being enough to does not need the chlorination in the permission time of the TiN in the nitride material with excessive chloridating gas to satisfied completeness.As mentioned above, compare, reduce the reductibility of environment in the chlorinating step, can reduce except TiCl with nitriding step
4The muriatic ratio that is generated in addition, and reaction conditions that can the selective chlorination step is to reduce this other muriatic generation, the existing description above the kinetics that these muriates generate.
At TiCl
4With any VOCl
3After the condensation, wherein residual chloridating gas and nitrogen can be recycled in the photochlorination vessel, as chloridating gas input or additional the adding.
As hereinafter discussing in more detail, the applicant finds that the ferrotianium slag that Witbank obtains, and rutile and ilmenite can carry out nitrogenize according to method of the present invention by Highveld steel and Van-adium corporation Limited.The nitrogenize matrix that this slag of nitrogenize is produced when X-ray diffraction analysis, provides clear and definite TiN crystalline phase, even have, also is other clear and definite crystalline phase of few any remarkable thing.Do not find to have titanium carbide or titanium carbonitride to form, also carbide or the carbonitride without any other metal forms.Therefore can think that the remaining component in nitriding step in the starting material slag forms vitreous non-crystalline state matrix phase, and the overwhelming majority (90%) (weight) or more in the titanium) can change nitride into.In next step chlorination, concerning any material, the muriate of generation has only TiCl
4, FeCl
3And VOCl
3, and these muriates all are to be easy to condensation and isolating as mentioned above.
Between nitriding step and chlorinating step, or beginning, present method can comprise the step by magnetic resolution iron in the material to be processed, and, for improving effect, can be with starting material at first with carbon and suitable fusing assistant, as CaCo
3, for example under 800-1200 ℃, handle, so that iron oxide reduction Cheng Tie.This step can reduce the Fecl that is finally produced
3The amount of waste product (is consulted: as people such as MacMillan, ' Proposed Process for Treatment of Low-Grade Titaniferous Ores ' (method that low-grade ilmenite is handled) US Department of the Interior, Bureau of Mines Report of Investigations 4638, January 1950).
When containing the titanium oxide composite materials and be a kind of blended metal oxide or titanate, for example, as ilmenite (FeOTiO
2), uhligite (CaOTiO
2), (Ca (Ti.Mg.Al) (Si.Al) for pyrgom
2O
6) or have picrocrichtonite (Mg0.2 TiO
2) and so on ore, nitriding step can cause in nitrogenize is carried out by the metal that produces one or more metallic states in the non-titanium metal that exists in described blended metal oxide or the titanate.
These metals can be used physical method before chlorinating step, as weight or magnetic resolution method, perhaps usefulness for example adopts leaching and so on the chemical process of hydrochloric acid, separates from this matrix.Therefore, usually, when the matrix that contains titanium nitride, when also containing the metal except that titanium, present method can comprise, before chlorination by the step of the metal of separation except that titanium in the described matrix.
Before chlorination, no matter be the reductibility that reduces environment, perhaps before chlorination, separate any metal that is produced, perhaps both's usefulness as mentioned above, all depend on the used raw-material performance of compound ferrotianium widely, and this can measure by routine test.In addition, as require in principle before chlorination, to eliminate fully reductibility environment and generation as described in any metal, but from considering that economically these steps are not proceed to completely.
The present invention also provides a kind of and makes a kind of titanium nitride that contains as its composition from the titaniferous composite materials, and is suitable for the matrix method that above-mentioned titanium reclaims of doing.
Therefore, according to a further aspect in the invention, provide a kind of production nitrogen titanium as its composition and be applicable to the method for the matrix that above-mentioned titanium value reclaims, this method comprises, be selected from compound metallurgical ferrotianium slag, ilmenite, uhligite, geikielite with and composition thereof the titaniferous composite materials in titanium carry out nitrogenize.
The present invention also relates to the titanium that reclaims at any time by above-mentioned recovery method, and the invention still further relates to by what aforementioned production method was produced and contain the matrix that titanium nitride is made its composition.
Referring now to accompanying drawing and example, the present invention is described by embodiment.
In the accompanying drawing:
Fig. 1 shows by the resulting ferrotianium slag of Highveld iron and steel and vanadium company limited (Steel and Vanadium Corporation Limited), uses Cuk
aThe X-ray diffraction style that ray records, its ° 2 θ scopes are 10-110 °;
Fig. 2 represents that to the slag of style shown in Figure 1, after following embodiment 1 nitrogenize, its ° 2 θ are the similar diffraction pattern of 32-80 ° of scope;
Fig. 3 represents, is used for being undertaken by the slag of embodiment 1 nitrogenize the schematic section of chlorating equipment;
Fig. 4 represents, according to the schematic section of the used equipment of embodiment 2 nitrogenize.
Embodiment 1
To contain 30% (weight) titanium value of having an appointment and (press TiO
2) the ferrotianium slag of Highveld Steel and Vanadium Corporation Limited grind and be crushed to the particle of particle diameter less than 1000 μ.With median size is the carbon of the dim shape of 0.5 μ, compares mixing in the ratio of 20% (weight) with slag.
The sample of slag and dim mixture is packed in the Alpha-alumina crucible, and be placed in the electrically heated tube furnace.This stove is repeated to vacuumize (4 times) until 20 torrs (Torr), and wash with high purity nitrogen (99.9998% (volume)).Defeated in stove with the flow velocity of the 40ml/min nitrogen gas stream that this is stable then.
Heat stove then lentamente, in 5 hours,, be heated to 1550 ℃, and 1550 ℃ of insulations 10 hours, so that the nitrogenization raw material mixture, and obtain the matrix of nitrogenize from room temperature with 5 ℃/minute basicly stable heating rate.Then stove is naturally cooled to room temperature, the nitrogenize matrix is carried out the X-ray diffraction analysis with the sample of raw mix (not nitrogenize).
The X-ray diffraction of raw mix be illustrated in Fig. 1 and the nitrogenize matrix be shown in Fig. 2.Fig. 1 represents that raw mix has quite high crystallization degree, and Fig. 2 shows, points out at the peak by many TiN clearly among Fig. 2, and except the basic ratio of TiN, the nitrogenize matrix is comparatively unbodied.
Before the nitrogenize, raw mix is a black, and after the nitrogenize in matrix, macroscopic spot to many light color.
Relate to Fig. 3 now, the nitrogenize matrix generally is chlorination in the equipment of several 10 expressions with reference.Equipment 10 comprises a tube electric heater 12, wherein settles one to be furnished with a glass inlet port pipe 16 and a tubular type glass reactor 14 that leads to the glass outlet pipe 18 of glass receiving flask 20.Bottle 20 has a glass gas outlet tube 22, and container 14 is equipped with thermopair 24 and a porous agglomerating glass disc 26.
During use equipment 10, the garden that 10 gram nitrogenize matrixes are placed in the container 14 is coiled, and will be with Cl
2The chloridating gas that exists is failed through managing 16 with the speed of 60 ml/min, and the temperature of chlorinator by well heater 12, with every grade of about speed of 50 ℃, is heated to 350 ℃ temperature step by step by room temperature simultaneously, in this case, and Cl
2Beginning and matrix reaction.When 1.5 hours afterreactions have tended to fully, with regard to stopped reaction.
In product receiving flask 20, obtain about 6 reaction product that restrain by managing 18, be yellowish brown liquid, also have a small amount of red solid thing.Decanting liq, the row element analysis of going forward side by side, analytical results is shown in table 1:
Table 1
Find out that from the analytical results that is shown in table 1 Al of detected minute quantity, Fe, Mg, Cr and Ca can disregard, and think and contain TiCl in the liquid
4, VCl
4And/or VOCl
3And SiCl
4Mixture and wherein be dissolved with number of C l
2, analytical results is shown in following table 2:
| Element | % (weight) |
| Cl | 75.8 |
| Ti | 20.9±0.3 |
| V | 0.93±0.03 |
| Si | 0.18±0.06 |
| Al | 0.01 |
| Fe | ＜0.01 |
| Mg | ＜0.005 |
| Cr | Do not detect |
| Ca | Do not detect |
Table 2
| Compound | % (weight) |
| TiCl 4 | 82,7 |
| VCl 4And/or VOCI 3 | 3,5 |
| SiCl 4 | 1,1 |
| | 12,7 (surpluses) |
For test reduces the feasibility of the reductibility carry out the chlorination environment, having in the presence of the carbon, according to reaction:
Chlorination is carried out at 350 ℃, and reaction continues more than 1 hour under each situation.Under first kind of situation, generate jonquilleous VOCl
3Product, and under second kind of situation, generate the VCl of avy blue
3Product.
Under the situation that does not have carbon to exist, revision test is not seen reaction, afterwards with 50 ℃ of elevated temperatures of each increase, and keeps 30 minutes under every rising temperature once, until 450 ℃ of top temperatures.Do not see any reaction takes place, this shows owing to the reducing environment that does not have carbon to provide, at least with regard to V
2O
5, suppressed to cause generating VoCl
3And VCl
3Pay reaction.
Embodiment 2
With titaniferous composite materials, slag among the embodiment 1 and ilmenite and the carbonaceous reducing agent that exists with coal and charcoal form, separated pulverizing is ground to the particle that maximum particle diameter is no more than 53 μ m.Then with starting material and carbonaceous reducing agent in required ratio uniform mixing, with the mixture of supplying raw materials.
The sample of different material mixture is respectively charged into electrically heated, and in two graphite boats in the horizontal pipe stove of sealing, this boat contains 5 kinds of samples of each 40 gram altogether.
With 255 ℃/hour speed heating stove, till the working temperature of placing the sample place is 1300 ℃, carry out keeping working temperature, then the naturally cooling stove in 3 hours processes of nitrogenize at sample.In the Total Test process, stable nitrogen gas stream (purity＞99% (volume)) is imported the stove of flowing through.
Under each situation, all prepared two kinds of raw mixs, a kind of is to contain raw-material titanium value (with TiO
2) be reduced to the carbon of the required stoichiometric ratio of titanium, another kind of then contain 100% excessive carbon.
Every part is that 40 four kinds of raw mix samples that restrain are placed in the boat, and by above-mentioned, using flow velocity is the nitrogen material gas of 620 ml/min, these samples of nitrogenize simultaneously.
The matrix reaction product of gained, qualitative with the X-ray diffraction method, and carry out quantitative chemical analysis to measure the TiN amount that is generated.Titanium content is by fusion, then uses atomic absorption spectrophotometer, and the nitrogen that exists is to measure with chemical analysis.
The used slag and the chemical ingredients of ilmenite are incorporated in the following table 3; And the conversion percentage of the TiN of gained is summarized in following table 4.
Used the same reference number of same section among Fig. 3 among Fig. 4.Reactor 14 is pipes of a kind of aluminosilicate, and manage 16,18 and 22 and bottle 20 all be stainless.Graphite boat is with 28 expressions, and heating unit is with 30 expressions.Porous aluminosilicate garden dish filter set is with 26 expressions, and it separates the entrance and exit of reactor 14, and well heater 12 is done as a whole, uses wrapped with insulation.
Table 3
aPrincipal mode: pyrgom (Ca (TiMg.Al) (Si, Al)
2O
6);
| Form | Starting material | |
| Ferrotianium slag (weight %) | Ilmenite (weight %) | |
| | 30,5 a | 48,8 |
| | 20,75 | 1,3 |
| | 14,10 | 1,0 |
| | 16,8 | 0,04 |
| Al 2O 3 | 13,65 | 0,7 |
| Cr 2O 3 | 0,19 | ＜0,01 |
| FeO | 5,15 | 47,9 |
| V 2O 3 | 1,05 | 0,12 |
| MnO | 0,69 | 0,82 |
Uhligite (caTiO
3) a small amount of form: pseudobrookite (Fe
2O
3TiO
2) ulvite (Fe
2TiO
4)
Table 4
| Starting material | Carbonaceous reducing agent | Reductive agent add-on (% of stoichiometry C ratio) | Be converted into the % (weight) of | |
| Slag | Charcoal | |||
| 100 | 73.6 | |||
| | Charcoal | 200 | 92.9 |
| | Coal | 100 | 73.8 | |
| | Coal | 200 | 92.7 | |
| | Charcoal | 100 | 72.9 | |
| | Charcoal | 200 | 94.9 | |
| | Coal | 100 | 75.8 | |
| | Coal | 200 | 91.6 |
Embodiment 1 has confirmed method of the present invention, is feasible to the ferrotianium slag that is used for being obtained by Highveld Steel and Vanadium Corporation Limited.Particularly, Fig. 2 shows, adopts 1550 ℃ of following nitrogenize, can be satisfactorily the titanium in the nitrogenize slag in high proportion, and high selectivity is arranged.Table 2 further shows, can only be contained VCl
4And/or VOCl
3, SiCl
4And Cl
2TiCl as impurity
4Chlorizate, and these impurity by the distillation can be from TiCl
4In be easy to separate, and obtain highly purified TiCl
4
If desired, this TiCl
4Be converted into TiO easily
2
Embodiment 2 shows, above-mentioned slag of nitrogenize and ilmenite are feasible at 1300 ℃, and use the excessive carbon of 100% stoichiometry, can obtain being higher than the high TiN transformation efficiency of 90% (weight).Can expect, best temperature, reductive agent ratio, the reaction times etc. will cause better conversion.
The advantage that the present invention gives prominence to is to provide a kind of method, can be used at least the slag among the embodiment, the ferrotianium slag is converted into value product, i.e. TiCl4/TiO
2 This slag produces as waste material in the production of the steel of Highveld iron and steel and vanadium Co., Ltd and vanadium, and single its volume is a potential environment difficult problem at least. This method has reduced the refuse amount that will throw away, and all is to allow on the ecology by any refuse that the inventive method produces, and to some industry, has potential purposes such as cement industry. In addition, for example, contain the ilmenite of quite low ratio titanium value, can be advantageously used for raw material in the method.
Claims (5)
1. one kind by containing titanium nitride as the method that reclaims titanium in the complex matrix of its composition, the steps include:
Titanium nitride in the chlorination matrix, and obtain containing the reaction product of titanium chloride;
From reaction product, separate titanium chloride, this method comprises the step of producing the titanium nitride matrix, said step is by the titanium value in the contained composite titanium in the nitrogenize starting material, and nitriding step is under 1000-1800 ℃ high temperature, under situation about having in the presence of the carbon of the reducing environment of providing, contact, having in the presence of the carbon of capacity, consuming existing all oxygen in the environment, and provide in the reducing material with TiO
2The titanium value of expression is the required stoichiometric excessive carbon of titanium, and this method comprises that also carbon mixes with starting material with the form of segmentation and the step of reducing environment is provided, the method is characterized in that after the nitrogenize with chlorination before, the step of separation carbon from matrix.
2. according to the method for claim 1, it is characterized in that combusting carbonaceous fuel makes combustible gas contact with starting material so that combustible gas to be provided in air, so that described high temperature to be provided, and provide reducing environment with the carbon monoxide form.
3. according to the method for claim 1, it is characterized in that the chlorination of titanium nitride is by being selected from Cl
2, HCl, CCl
4, SCl
2With and composition thereof chloridating gas, under 350-450 ℃ temperature, contact, and obtain titanium chloride with titanium nitride.
4. according to the method for claim 3, it is characterized in that chloridating gas is Cl
2, it forms with nitrogen dilution and contains 20-80% (volume) Cl
2Mixed gas.
5. according to the method for claim 1, it is characterized in that the matrix that contains titanium nitride also contains the metal except that titanium, this method is included in before the chlorination by the step of separating the metal except that titanium in the described matrix.
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|---|---|---|---|
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| CA2762897C (en) * | 2009-05-29 | 2013-08-20 | Hitachi Metals, Ltd. | Method for producing titanium metal |
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| GB795386A (en) * | 1955-06-24 | 1958-05-21 | Ici Ltd | Improvements in or relating to the electrolytic production of titanium |
| CN1033264A (en) * | 1987-10-27 | 1989-06-07 | 冶金工业部攀枝花钢铁公司钢铁研究院 | The method of preparing titanic chloride using carbon-containing slag |
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|---|---|---|---|---|
| US3060002A (en) * | 1959-09-25 | 1962-10-23 | Dow Chemical Co | Pressure leaching of titaniferous material |
| DE2103255C3 (en) * | 1971-01-25 | 1974-05-30 | Parlee Anderson Corp., Burlingame, Calif. (V.St.A.) | Carbothermal process for reducing an oxide from a reactive metal |
| SE431231B (en) * | 1982-05-28 | 1984-01-23 | Skf Steel Eng Ab | WAY TO Separate and Extract Iron and Its Alloys from Fine-grained Oxide Raw Materials |
-
1991
- 1991-07-22 NZ NZ239070A patent/NZ239070A/en not_active IP Right Cessation
- 1991-07-24 DE DE4124547A patent/DE4124547C2/en not_active Expired - Lifetime
- 1991-08-01 CN CN91105786A patent/CN1037982C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB795386A (en) * | 1955-06-24 | 1958-05-21 | Ici Ltd | Improvements in or relating to the electrolytic production of titanium |
| CN1033264A (en) * | 1987-10-27 | 1989-06-07 | 冶金工业部攀枝花钢铁公司钢铁研究院 | The method of preparing titanic chloride using carbon-containing slag |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108677025A (en) * | 2018-07-12 | 2018-10-19 | 重庆大学 | The method that titanium-containing blast furnace slag carries titanium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1069072A (en) | 1993-02-17 |
| NZ239070A (en) | 1992-11-25 |
| DE4124547C2 (en) | 1997-04-30 |
| DE4124547A1 (en) | 1992-01-30 |
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