AU2021254548B2 - Method for preparing high TiO2 grade material from ilmenite middlings - Google Patents
Method for preparing high TiO2 grade material from ilmenite middlings Download PDFInfo
- Publication number
- AU2021254548B2 AU2021254548B2 AU2021254548A AU2021254548A AU2021254548B2 AU 2021254548 B2 AU2021254548 B2 AU 2021254548B2 AU 2021254548 A AU2021254548 A AU 2021254548A AU 2021254548 A AU2021254548 A AU 2021254548A AU 2021254548 B2 AU2021254548 B2 AU 2021254548B2
- Authority
- AU
- Australia
- Prior art keywords
- ilmenite
- middling
- materials
- reduced
- ferrotitanium
- 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.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 230
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 239000000463 material Substances 0.000 title claims abstract description 199
- 238000000034 method Methods 0.000 title claims abstract description 110
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims abstract description 143
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 101
- 239000011707 mineral Substances 0.000 claims abstract description 101
- 230000009467 reduction Effects 0.000 claims abstract description 81
- 238000007885 magnetic separation Methods 0.000 claims abstract description 69
- 230000008569 process Effects 0.000 claims abstract description 53
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 229910001773 titanium mineral Inorganic materials 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 177
- 239000010936 titanium Substances 0.000 claims description 70
- 229910052719 titanium Inorganic materials 0.000 claims description 69
- 229910052742 iron Inorganic materials 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- 238000002386 leaching Methods 0.000 claims description 27
- 238000001465 metallisation Methods 0.000 claims description 27
- 239000002893 slag Substances 0.000 claims description 23
- 238000003723 Smelting Methods 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- 239000002223 garnet Substances 0.000 claims description 9
- -1 that is Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011651 chromium Substances 0.000 abstract description 123
- 229910052804 chromium Inorganic materials 0.000 abstract description 116
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 82
- 239000012141 concentrate Substances 0.000 abstract description 81
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 230000001603 reducing effect Effects 0.000 abstract description 15
- 238000009776 industrial production Methods 0.000 abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 235000010755 mineral Nutrition 0.000 description 87
- 235000010215 titanium dioxide Nutrition 0.000 description 79
- 238000006722 reduction reaction Methods 0.000 description 67
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 56
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 55
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 38
- 238000011084 recovery Methods 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 31
- 239000004615 ingredient Substances 0.000 description 30
- 239000000126 substance Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 23
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 20
- 239000000395 magnesium oxide Substances 0.000 description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 230000005389 magnetism Effects 0.000 description 19
- 239000000292 calcium oxide Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 239000012463 white pigment Substances 0.000 description 17
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000002006 petroleum coke Substances 0.000 description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- NJXPYZHXZZCTNI-UHFFFAOYSA-N 3-aminobenzonitrile Chemical compound NC1=CC=CC(C#N)=C1 NJXPYZHXZZCTNI-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000005660 chlorination reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003245 coal Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910001608 iron mineral Inorganic materials 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 201000009409 embryonal rhabdomyosarcoma Diseases 0.000 description 4
- 229910052595 hematite Inorganic materials 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910001919 chlorite Inorganic materials 0.000 description 3
- 229910052619 chlorite group Inorganic materials 0.000 description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011019 hematite Substances 0.000 description 3
- 229910052622 kaolinite Inorganic materials 0.000 description 3
- 229910052655 plagioclase feldspar Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910009973 Ti2O3 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052849 andalusite Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000006148 magnetic separator Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000615 nonconductor Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012932 thermodynamic analysis Methods 0.000 description 2
- 239000001038 titanium pigment Substances 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 2
- 229910052613 tourmaline Inorganic materials 0.000 description 2
- 239000011032 tourmaline Substances 0.000 description 2
- 229940070527 tourmaline Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003430 FeCr2O4 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
- 229910020105 MgCr2O4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910009815 Ti3O5 Inorganic materials 0.000 description 1
- 229910010253 TiO7 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052850 kyanite Inorganic materials 0.000 description 1
- 239000010443 kyanite Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011031 topaz Substances 0.000 description 1
- 229910052853 topaz 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
- C22B1/00—Preliminary treatment of ores or scrap
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
-
- 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
- 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
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- C22B34/00—Obtaining refractory metals
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
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Abstract
The present disclosure discloses a method for preparing ahigh TiO2 grade
material from ilmenite middling. The ilmenite middling include titanium minerals
and weak magnetic gangue minerals, and the method includes the following
steps: S1, making the ilmenite middling be in contact with a reducing agent for
performing deep reduction, so that Fe 2 + and/or Fe 3+ in the titanium minerals is
completely or partially reduced into FeO, while Fe2+ and/or Fe 3+ in the weak
magnetic gangue minerals remains in an unreduced state to obtain reduced
ilmenite middling; S2, performing magnetic separation on the reduced ilmenite
middling to obtain reduced ferrotitanium materials and tailings containing the
weak magnetic gangue minerals through separation; and S3, further preparing
the reduced ferrotitanium materials to obtain the high TiO2 grade material.
According to the present disclosure, by increasing the magnetic difference
between the reduced ferrotitanium materials and the weak magnetic gangue
minerals, magnetic separation is facilitated. Then the deep reduction for
ilmenite middling purification is combined with the deep reduction for preparing
the high TiO2 grade material from ilmenite, so that a process route is shortened,
a production cost is reduced, and industrial production is facilitated.
(28403934_1):AXG
3/3
High-chromium ilmenite middlings
reducing agent I deep reduction
agnetic rough chromium concentrate (weak/non
concentration magnetic minerals)
magnetic
concentrations
reducing ferrotitanium materials
(strong magnetic minerals)
FIG. 5
High-chromium ilmenite middling,
reducing agent deep reduction I
agnetic chromium concentrate I
oncentratio (weak/non-rnagnetic minerals)
magnetic
concentratio
reducing agent deep reduction i1
magneticchromium concentrate Il
rough
concentratiO (weak/non-magnetic minerals)
rnagnetic
concentration
reducing ferrotitanium materials
(strong magnetic minerals)
FIG. 6
(28403934_1):AXG
Description
3/3
High-chromium ilmenite middlings
reducing agent I deep reduction
agnetic rough chromium concentrate (weak/non concentration magnetic minerals)
magnetic concentrations
reducing ferrotitanium materials (strong magnetic minerals)
FIG. 5
High-chromium ilmenite middling,
reducing agent deep reduction I
agnetic chromium concentrate I oncentratio (weak/non-rnagnetic minerals)
magnetic concentratio
reducing agent deep reduction i1
magneticchromium concentrate Il rough concentratiO (weak/non-magnetic minerals)
rnagnetic concentration
reducing ferrotitanium materials (strong magnetic minerals)
FIG. 6
(28403934_1):AXG
Method for Preparing High TiO2 Grade Material from Ilmenite Middlings
Cross-reference to Related Application The present disclosure claims the priority to the Chinese patent application with the filing number 202011186492.X entitled "Method for Preparing high TiO2 Grade Material from ilmenite middling" filed on October 30, 2020 with the Chinese Patent Office, the contents of which are incorporated herein by reference in entirety. Technical Field The present disclosure belongs to the technical field of metallurgy and mineral processing, and in particular, relates to a method for preparing a high TiO2 grade material from ilmenite middlings. Background Art The titanium white pigment is a white pigment with the best performance at present, and is widely applied in the fields such as coating, rubber, plastic, papermaking, and printing ink. There are mainly two processes for production of titanium white pigment, sulfuric acid process and chlorination process. The production process of titanium white pigment by the chlorination process is an internationally recognized new generation of advanced technology for replacing the sulfuric acid process due to its environment friendly and high product quality during its production process. Currently, the titanium white pigment production by the sulfuric acid process in China is stepping to medium-high level, the application fields of the product realize full coverage, the titanium white pigment produced by the chlorination process realizes breakage and is developed in depth and breadth in recent years, and the production process gains substantive progress. It is believed that the Chinese titanium white pigment produced by the chlorination process will enter a rapid development period in the future years, subsequently, the demand for high TiO2 grade materials such as raw material synthetical rutile and high-titanium slag is also increasing. Ilmenite, a main feedstock for refining titanium and producing titanium white pigment, has a main component of FeTiO3, but meanwhile contains other impurity minerals containing impurity elements such as CaO, MgO, Si2, A1203, MnO2, V205, and Cr203, and the presence of these impurity elements will affect the quality of ilmenite product. The titanium white pigment produced by the chlorination process has quite strict requirements to titanium feedstock, especially higher requirement to impurity content, such as CaO, MgO, SiO2, A1203, MnO2, V205and Cr203. Generally speaking, if a trace amount of impurities such as iron, cobalt, chromium, and copper are adopted into the titanium white pigment, the whiteness of the titanium white pigment will be reduced, because the existence of ions of impurities thereof, especially metal oxidate ions, will cause the crystal structure of the titanium white pigment to be distorted and lose symmetry, and the rutile type titanium white is more sensitive to the appearance of impurities, wherein if the content of chromium oxidate (Cr203) in the high TiO2 grade material is higher than 0.15%, the high TiO2 grade material cannot be used to produce the titanium white by the chlorination process. (28403934_1):AXG
However, with the continuous increasing of production capacity of titanium white pigment and continuous mining and use of ilmenite, the ilmenite directly used to produce high TiO2 grade materials is gradually decreased. However, there are a large amount of high-chromium titanium resources in the world at present, for example, ilmenite in wide alluvial and coastal sedimentary mineral deposits along or near the coast of the Mediterranean beach along convex Nile Delta has a higher chromium content, and a large amount of chromium containing titanium resources exist in Mozambique, Australia, and Vietnam. Studying how to use ilmenite with a high impurity content and a low titanium grade to produce high-quality feedstock by the chlorination process haS is important for the development of the chlorination process.
The beach sands is the most industrially valuable titanium placer deposit, 30% of the ilmenite in the world comes from the beach sands, the beach sands mainly has coastal sedimentary placer, the beach sands has the characteristics of varied mineral types, high monomer dissociation degree, uniform particles, a small mud content and so on, and main useful minerals include ilmenite, zirconite, rutile, monazite, leucoxene, anatase and so on. The main impurity minerals include: chromite, titanaugite, maghemite, iron concretion, limonite, hematite, pyrite and so on. The main gangue minerals include quartz, feldspar, tourmaline, garnet, andalusite, topaz, kyanite, apatite, kaolin and so on (chromite, titanaugite and so on are also gangue minerals in beach sands). A common refining process of beach sands is a combined procedure of conventional gravity separation, dry magnetic separation, and electric separation. Table 1 Physical Properties of Weak Magnetic Gangue Minerals and Ilmenite
Mineral Magnetism (X1O- 9M 3/Kg) specific Gravity (g/cm3) Conductivity
Ilmenite (FeTiOn -315 -4,6 Conductor Chromite ((Fe, Mg)Cr2O4) -287 ~4.5 Conductor
Titanaugile 3 Ca(Mg, Fe2, Fe +,Al, Ti)(Si, AI)206 130 - Nonconductor
Garnet (Fe, Mg, Mn)3(AI, Fe)2[SiO43 -70 -4.1 Nonconductor
For the titanium resources containing weak magnetic gangue minerals, as the physical properties (as in Table 1) of the weak magnetic gangue minerals such as chromite, titanaugite, garnet, and ilmenite are quite close, it is quite difficult to separate such minerals by a conventional method mineral processing, and most of the weak magnetic gangue minerals are enriched along with the ilmenite, so that the ilmenite concentrate cannot be utilized as the impurity content in the ilmenite concentrate cannot meet the requirement of being used as the titanium white pigment feed stock, causing waste of resources. At present, the ilmenite concentrate (middling) of this type of titanium resource can only be stockpiled in a form of tailing as the chromium content exceeds the requirement as a feed stock for titanium white pigment. The chromium in the ilmenite concentrate (middling) generally exists in the form of (284039341):AXG chromite, and belongs to monomer dissociated minerals. As the physical properties of ilmenite and chromite are similar, the chromite in the ilmenite cannot be well separated by adopting the conventional modes of gravity separation, magnetic separation, electric separation or combination of the three modes, therefore, how to remove impurities in the ilmenite and obtain high quality ilmenite concentrate has extremely important significance for comprehensive utilization of titanium raw materials. At present, for the treatment of this type of ilmenite middling, the ilmenite in the ilmenite middling is mainly modified by oxidization and magnetization, but the sorting effect is unfavorable due to the fact that the process conditions are difficult to control. Austpac Resources N.L. researches two ilmenite magnetizing and roasting methods, which are called as ERMS roasting method and LTR roasting method, respectively. The ERMS roasting method (US5595347 "Process for Separating Ilmenite") is to roast ilmenite for about 60 min at high temperature (750-950 °C) at a controlled oxygen partial pressure, and the roasted minerals are cooled under an anoxic condition. The roasting increases the magnetic susceptibility of ilmenite, TiO2 in the minerals is transformed into rutile and is acid-insoluble, and the roasted minerals are easy to magnetically separate to remove gangue minerals, thus improving the quality of ilmenite concentrate. Such roasted concentrate is suitable for producing synthetical rutile or smelting titanium slag. The LTR roasting method is to roast ilmenite at a low temperature of lower than 650 °C for 20-30 min, the roasting increases the magnetic susceptibility of ilmenite, TiO2 in the minerals is not transformed into rutile and is acid-soluble, and the roasted minerals are also easy to magnetically separate to remove gangue minerals, thus improving the quality of ilmenite concentrate. Such roasted concentrate is suitable for production of titanium white pigment by the sulfuric acid process. The ERMS roasting method is strong oxidation-weak reduction roasting, and the roasted minerals are used to prepare synthetical rutile by a hydrochloric acid leaching method. In "Thermodynamic Analysis on Ilmenite Separation by Magnetic Roasting" (Iron Steel Vanadium Titanium, Vol. 34, No. 3, June 2013) of Liu Yunlong et al., ilmenite is oxidized and roasted by oxygen or air to generate Fe23 and Fe2TiO which then may be reduced into Fe304 with CO of lower concentration, followed by ball milling by a ball mill, and then iron concentrate and titanium slag may be obtained just by means of magnetic separation, achieving the purpose of iron and titanium oxidate separation. In "Experimental Research on Concentration of Certain Ilmenite Abroad" (master thesis of Kunming University of Science and Technology in 2015) of Wang Mo et al., mixed rough concentrate of ilmenite and chromite is oxidized and roasted by a rotary kiln, a fluidized bed or a boiling furnace under following roasting process parameters: 770 °C of operation temperature, 3.0 Kg/h of feeding speed, and 36 minutes of corresponding average retention time, and naturally cooled, then ilmenite may be well enriched. The enriched minerals after oxidization and roasting is subjected to dry separation on a dry magnetic separator with a magnetic field of 0.3 t, then ilmenite concentrate may be obtained with the TiO2 grade of 47.94%, the recovery of 78.52%, and with Cr203 of 0.23%. (28403934_1):AXG
Chinese patent CN103316761B discloses a separation method for minerals containing ilmenite and chromite. This patent is mainly directed to beach heavy minerals sands containing ilmenite and chromite, wherein ilmenite and chromite are respectively enriched into chromium-containing ilmenite middling by mineral pre-processing, the magnetism of ilmenite is increased through oxidization and roasting, and chromite and ilmenite are separated by magnetic separation, to obtain chromium concentrate and titanium concentrate.
Current researches mainly focus on increasing the magnetism of ilmenite by a weak oxidation method, and removing chromite and so on by a magnetic separation method to produce high-grade ilmenite concentrate. The technology for increasing magnetism by weak oxidation of ilmenite has relatively strict requirements to oxidation temperature, oxygen content, and time, is not beneficial to large-scale industrial production, and meanwhile a ilmenite concentrate purification process and a subsequent ilmenite concentrate deep processing process are not combined. The reference to any prior art in this specification is not and should not be taken as an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge. Summary
A desirable outcome of the present disclosure lies in providing a method for preparing a high TiO2 grade material from ilmenite middlings to overcome deficiencies in the prior art. The desirable outcome of the present disclosure is realized or at least substantially ameliorated by the following technical solution. According to one aspect, the present disclosure provides a method for preparing a high TiO2 grade material from ilmenite middling, the ilmenite middling comprising titanium minerals and weak magnetic gangue minerals, wherein the method comprises following steps: S1, making the ilmenite middling in contact with a reducing agent for performing deep reduction, so that Fe 2 + and/or Fe 3+ in the titanium minerals is completely or partially reduced into FeO, while Fe 2+ and/or Fe 3 + in the weak magnetic gangue minerals remain in an unreduced state, so as to obtain reduced ilmenite middling, and a temperature for the deep reduction is 800-1100 °C, and the deep reduction lasts for 0.5-4 h; S2, performing magnetic separation on the reduced ilmenite middling to obtain reduced ferrotitanium materials and tailings containing the weak magnetic gangue minerals through separation; and S3, further preparing the reduced ferrotitanium materials to obtain the high TiO2 grade material.
4a
According to a second aspect, the present invention provides a high TiO2 grade material from ilmenite middling prepared according to the method of the first aspect. In one embodiment, a method for preparing a high TiO2 grade material from ilmenite middlings, wherein the ilmenite middlings include titanium minerals and weak magnetic gangue minerals, and the method includes the following steps: S1, making the ilmenite middlings in contact with a reducing agent for performing deep reduction, so that Fe 2 + and/or Fe 3+ in the titanium minerals is completely or partially reduced into FeO, while Fe 2+ and/or Fe 3+ in the weak magnetic gangue minerals remains in an unreduced state to obtain reduced ilmenite middlings; S2, performing magnetic separation on the reduced ilmenite middlings to obtain reduced ferrotitanium materials and tailings containing the weak magnetic gangue minerals through separation; and
S3, preparing the reduced ferrotitanium materials to obtain the high TiO2 grade material. Preferably, the titanium minerals of the ilmenite middlings include one or a combination of more selected from ilmenite or rutile, the weak magnetic gangue minerals include one or a combination of more selected from picotite, titanaugite or garnet, and the ilmenite middlings at least contain one titanium mineral and one weak magnetic gangue mineral. Preferably, the high TiO2 grade material is synthetic rutile or high-titanium slag; and the synthetic rutile is prepared by an acid leaching or rusting process.
Preferably, when the high TiO2 grade material is prepared by the acid leaching method, a metallization rate of the adopted reduced ferrotitanium materials is 85% or more; and when the high TiO2 grade material is prepared by the rusting process, the metallization rate of the adopted reduced ferrotitanium materials is 90% or more. Preferably, the high TiO2 grade material is prepared by the acid leaching method under the following condition: the reduced ferrotitanium materials and a leaching acid react for 0.5-2 h at normal pressure, at a reaction temperature of 20-60 °C, wherein a mass volume ratio of the reduced ferrotitanium materials to the leaching acid is 1:(2-5), and mass fraction concentration of the leaching acid is 13-25%. Preferably, the high TiO2 grade material is prepared by the rusting process under the following condition: the reduced ferrotitanium materials and a rusting liquid react for 2-6 h under a condition of introducing air, to obtain primary synthetic rutile; the reaction temperature is 30-110 °C, a mass ratio of the reduced ferrotitanium materials to the rusting liquid is 1:(2-8), the rusting liquid is an ammonium salt aqueous solution, an ammonium salt in the rusting liquid is one or a mixture of two of NH4CI and (NH4)2SO4, and ammonium salt concentration of the rusting liquid is 0.05-4 mol/L; and then the primary synthetic rutile and an inorganic acid with mass fraction of 15 %, at a solid-to-liquid ratio of 1:(3-6), react for 3-5 h at 80-100 °C to obtain the synthetic rutile. Preferably, the high-titanium slag is prepared under the following condition: smelting the reduced ferrotitanium materials and a reducing agent in an electric furnace at a smelting temperature of 1600-1750 °C. Preferably, in step S1, the deep reduction temperature is 800-1100 °C, and the deep reduction lasts for 0.5-4 h. Preferably, the reduced ferrotitanium materials obtained after the deep reduction and magnetic separation in step S2 is further subjected to at least one time of deep reduction and magnetic separation. Preferably, the temperature of the later deep reduction is not lower than that of the former deep reduction. Preferably, the deep reduction is performed twice, the temperature in the first deep reduction is 800-1000 °C, and the temperature in the second deep reduction is 1000-1100 °C. The present disclosure is distinguished from the prior art as follows. The ERMS roasting method (US5595347 "Process for Separating Ilmenite") is to roast ilmenite for about 60 min at high temperature (750-950 °C) at a controlled oxygen partial pressure, and the roasted minerals are cooled under an anoxic condition. The roasting increases the magnetic susceptibility of ilmenite. The method for increasing the magnetic susceptibility of ilmenite by this technology is still oxidation. FeO in ilmenite is converted into magnetite (Fe304). As the technology controls the oxygen partial pressure to avoid further (28403934_1):AXG oxidation of magnetite (Fe304) into nonmagnetic hematite (Fe2O3), this technology is carried out under oxidizing atmosphere conditions. In the present disclosure, the ilmenite is reduced into metallic iron under the condition of reducing atmosphere. In "Experimental Research on Concentration of Certain Ilmenite Abroad" of Wang Mo et al., oxidization and roasting are performed by a rotary kiln, a fluidized bed or a boiling furnace under the roasting process parameter of 770 °C so as to achieve the purpose of increasing the magnetism of ilmenite. In the present disclosure, the ilmenite is reduced into metallic iron under the condition of reducing atmosphere so as to achieve the purpose of increasing the magnetism of ilmenite. In "Thermodynamic Analysis on Ilmenite Separation by Magnetic Roasting" (Iron Steel Vanadium Titanium, Vol. 34, No. 3, June 2013) of Liu Yunlong et al., ilmenite is oxidized and roasted by oxygen or air to generate Fe2O3 and Fe2TiO5 which then may be reduced into Fe304 with CO of lower concentration, followed by ball milling by a ball mill, and then iron concentrate and titanium slag may be obtained by means of magnetic separation, achieving the purpose of iron and titanium separation. Although this technology is performed in a reducing atmosphere, reducing iron into magnetic ferroferric oxide, but not metallic iron, is fundamentally different from the present disclosure. In the present disclosure, by deeply reducing the titanium minerals in the ilmenite middling into the reduced ferrotitanium materials containing metallic iron, the weak magnetic gangue minerals, such as chromite, still remain in an unreduced state and an original crystalline form, thus the reduction increases the magnetic difference between the reduced ferrotitanium materials and the weak magnetic gangue minerals, facilitating the magnetic separation. Then the deep reduction for concentrating the ilmenite middling is combined with the deep reduction for preparing the high TiO2 grade material from ilmenite, the process route is shortened, the production cost is reduced, and the industrial production is facilitated. As used herein, the term "comprising" means "including." Variations of the word "comprising", such as "comprise" and "comprises," have correspondingly varied meanings. Any description of publications, or statements herein derived from or based on those publications, is not an admission that the publications or derived statements are part of the prior art base or common general knowledge of the relevant art. Brief Description of Drawings FIG. 1 shows X-ray diffraction (XRD) of high-chromium ilmenite middling; FIG. 2 shows X-ray diffraction (XRD) of reduced high-chromium ilmenite middling; FIG. 3 shows X-ray diffraction (XRD) of reduced ferrotitanium material; FIG. 4 shows X-ray diffraction (XRD) of chromium concentrate; (28403934_1):AXG
FIG. 5 is a flowsheet of first-stage deep reduction/magnetic separation; and FIG. 6 is a flowsheet of second-stage deep reduction/magnetic separation. Detailed Description of Embodiments The ilmenite middling containing weak magnetic gangue minerals, due to too high content of impurities, cannot satisfy the requirements for producing titanium white pigment by the sulfuric acid process or producing raw materials for the chlorination process. Impurities thereof are mainly CaO, MgO, SiO 2
, Cr203, etc., and the impurities are mainly from the weak magnetic gangue minerals, such as chromite, titanaugite, and garnet.
The present disclosure discloses a method for preparing a high TiO2 grade material from ilmenite middling, wherein the ilmenite middling include titanium minerals and weak magnetic gangue minerals, and the method includes the following steps: S1, making the ilmenite middling be in contact with a reducing agent for performing deep reduction, so that Fe 2 + and/or Fe 3+ in the titanium minerals is completely or partially reduced into FeO, while Fe 2+ and/or Fe 3+ in the weak magnetic gangue minerals remains in an unreduced state to obtain reduced ilmenite middling, wherein the reducing agent may adopt one or a combination of more of coal, petroleum coke, CO or H2; S2, performing magnetic separation on the reduced ilmenite middling to obtain reduced ferrotitanium materials and tailings containing the weak magnetic gangue minerals through separation; and S3, further preparing the reduced ferrotitanium materials to obtain the high TiO2 grade material. Iron in natural oxidized minerals generally exists in a form of FeO, Fe304, or Fe203, only magnetite Fe304 (FeO-Fe2O3) has strong magnetism, and the remaining ferrous oxide (FeO) and hematite (Fe203) are weak magnetic minerals. Therefore, the difference in the reducibility of iron in various minerals can be utilized to selectively reduce the iron in a given mineral into Fe304 or elemental iron to increase the magnetism of the minerals. Since the generation conditions of magnetite (Fe304) are too narrow to control, the present disclosure adopts the manner of deep reduction to reduce iron in the titanium minerals completely or partially into elemental iron so as to increase the magnetism of the ilmenite, while the weak magnetic gangue minerals such as Fe 2+ and/or Fe3+ of chromite remain in the unreduced state, the two may be easily separated through magnetic separation, and finally the magnetic reduced ferrotitanium materials and tailings of non-/weak magnetic gangue minerals are obtained; and the reduction of ferrotitanium materials is combined with the deep reduction for preparing the high TiO2 grade material from titanium mineral, to obtain the high TiO2 grade materials, which shortens the process route, reduces the production cost, and facilitates industrial production. A process for preparing high TiO2 grade materials may employ conventional acid leaching, rusting process, electric furnace smelting and separating methods, etc.
(28403934_1):AXG
As could be understood by a person skilled in the art, the ilmenite middling are magnetically separated concentrate obtained from ilmenite placer titanium resources by a conventional mineral processing method such as gravity separation and magnetic separation, generally mainly contain titanium minerals (ilmenite, weathered ilmenite, rutile, etc.), iron minerals (titanium-magnetite, martite, haematite, etc.), weak magnetic gangue minerals (chromite, picotite, titanaugite, garnet, etc.), and in addition, generally further contain a small amount of common gangue minerals of sand type ilmenite such as zirconite, quartz, plagioclase, kaolinite, and chlorite. Through the deep reduction, ilmenite, weathered ilmenite, iron oxide minerals, rutile, etc. enter the reduced ferrotitanium materials; Fe 2+and/or Fe 3 + in the iron minerals are also completely or partially reduced into FeO, and when the magnetic separation is performed on the reduced ilmenite middling in step S2, FeO, together with the ilmenite, is separated from the weak magnetic gangue minerals such as chromite, the rutile generally co-exists with the ilmenite, and enters the reduced ferrotitanium materials along with the ilmenite. The weak magnetic gangue minerals in the ilmenite middling generally contain chromite, and in addition to chromite, generally further contain one or more of picotite, titanaugite, or garnet, and these weak magnetic gangue minerals together enter the tailings through magnetic separation. Gangue minerals such as zirconite, quartz, plagioclase, kaolinite, or chlorite are also separated from the ilmenite together with the weak magnetic gangue minerals such as chromite, to enter the tailings, when the magnetic separation is performed on the reduced ilmenite middling in step S2. Therefore, the tailings having undergone the magnetic separation generally contain chromite, picotite, coal ash, coal (when coal, petroleum coke, etc., are adopted for reduction, coal ash and remaining coal, petroleum coke will be generated) and a small amount of reduced ferrotitanium materials, zirconite, quartz, plagioclase, kaolinite, chlorite and other common gangue minerals of sand type ilmenite. Elemental iron greatly improves the magnetism of ferrotitanium materials and increases the magnetic difference from weak magnetic gangue minerals. The higher the metallization rate of the reduced ferrotitanium materials is, the stronger the magnetism of the ferrotitanium materials is, and the larger the magnetic difference between the ferrotitanium materials and the gangue minerals is, the better the magnetic separation is. However, when the metallization rate (percentage of metallic iron in total iron, Fe0 /TFe x 100%) of the reduced ferrotitanium materials is excessively high, the reduction of the ferrotitanium materials under the effect of a magnetic field tends to produce phenomena such as magnetic chain and magnetic agglomeration, and the magnetic chain and the magnetic agglomeration on the contrary will reduce the separation effect of magnetic separation. Therefore, the metallization rate of the reduced ferrotitanium materials is preferably 5-95%. Through the deep reduction in step S1, Fe 2+ and/or Fe 3 + in ilmenite is completely or partially reduced into FeO, while Fe2+ and/or Fe3+ in the weak magnetic gangue minerals such as chromite remain in the unreduced state. A suitable deep reduction condition needs to be selected. By preference, the deep (28403934_1):AXG reduction temperature is 800-1100 °C, and the deep reduction lasts for 0.5-4 h. When the reducing agent is a solid reducing agent such as coal and petroleum coke, an addition amount is preferably 10-30% (mass ratio) of the ilmenite middling, and when the reducing agent is a gas reducing agent such as CO and H2, the contents of CO and H in an exhaust gas are controlled to be greater than or equal to 3%. Reduced ferrotitanium materials (FeTiO3-TiO2-Fe, FeTiO3-Ti2O3-2Fe, FeTiO3-Ti2O3-2Fe, etc.) are prepared through thermal reduction reaction of ilmenite (FeTiO3) with a reducing agent (such as coal), the reduced ferrotitanium materials mainly consist of reduced FeTiO3, Fe, TiO2, Ti2O3, etc., and the content of each component mainly depends on the reducing conditions (temperature and period). The higher the reduction temperature is and the longer the period is, the higher the Fe, TiO2 contents are and the lower the FeTiO3 content is. Reducing equipment is usually a rotary kiln, and other reducing equipment such as a boiling bed may also be used. The reducing agent (such as coal) mainly functions in two aspects, one is to provide the CO required for the reaction, and the other is to provide the heat required for the reaction. Main reactions of the ilmenite and the reducing agent coal in the rotary kiln are as follows:
FeTiO3+C=TiO2-Fe+CO
FeTiO3+CO=TiO2-Fe+CO2
3FeTiO3+4C=Ti3O53Fe+4CO 3FeTiO3+4CO=Ti3O5-3Fe+4CO2
2FeTiO3+3C=Ti2O3-2Fe+3CO
2FeTiO3+3CO=Ti2O3-2Fe+3CO2
2FeTiO3+C=FeTi205-Fe+CO 2FeTiO3+CO=FeTi205-Fe+CO2
Fe2O3+3C=2Fe+3CO
CO2+C=2CO C+O2=2CO
Under the condition of 800-1100 °C, metallic iron is precipitated more or less from the ilmenite, and the ilmenite particles remain in an original state and coexist with the metallic iron, thereby increasing the magnetism of the ilmenite in geometric grade, while weak magnetic gangue minerals such as chromite can only be reduced at 1100-15000 C to generate elemental iron. Reaction formulas involved are as follows:
FeCr2O4+C=Fe-Cr2O3+CO
3FeCr2O4+4C=3Fe-2Cr3O4+4CO
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Therefore, since the reduction activity of ilmenite is higher than the reduction activity of chromite, when ilmenite and chromite simultaneously exist, ilmenite is reduced before chromite under the conditions of the present disclosure. Under conditions of 800 °C-1100 °C and no more than 4 h of reduction, the chromite retains the original crystal lattice and is still a weak magnetic mineral, then it is readily separated from the reduced ferrotitanium materials through magnetic separation. Before the reduction of the ilmenite middling in step S1, oxidization roasting may also be performed first so as to improve the reducing activity of the ilmenite in the ilmenite middling. The oxidization roasting of the ilmenite middling are to oxidize iron in the ilmenite to generate TiO2 and Fe2O3. The reducing activity of Fe2O3 is higher than that of FeTiO3 (ilmenite), then the reduction of Fe2O3 is easier to control. The oxidation condition is preferably 600-1000 °C, and the roasting lasts for 0.5-2 h. When the activity of ilmenite middling is lower, it is preferable to use a method of performing oxidation first to increase the activity thereof, and then performing deep reduction. After the oxidation activity is improved, a lower reduction temperature and/or a shorter reduction period of time may be adopted in the subsequent deep reduction. Deep reduction of ilmenite middling is to selectively reduce ilmenite into ferrotitanium materials containing iron metal, while weak magnetic gangue minerals such as chromite still retain the original crystal lattice (weak magnetism). The deep reduction of ilmenite middling increases the magnetic difference between the ferrotitanium materials and the chromite, and is beneficial to the separation effect of magnetic separation. Certainly, the metallic iron in the ferrotitanium materials is a strong magnetic substance, the phenomena of magnetic chain and magnetic agglomeration easily occur in the magnetic field, therefore, the effect of separating the chromite by magnetic separation also will be affected. Hence, multi-stage reduction-magnetic separation is beneficial to the magnetic separation effect, the multi-stage reduction-magnetic separation (FIG. 6) process is an extension of the first stage reduction-magnetic separation (FIG. 5) process, and is to further perform at least one time of deep reduction and magnetic separation on the reduced ferrotitanium materials obtained after deep reduction and magnetic separation, to obtain the multi-stage reduced ferrotitanium materials. Preferably, the temperature of the later deep reduction is not lower than that of the former deep reduction. If the first-stage reduction adopts a low temperature for reduction (for example, 800°C-1000°C), second-stage reduction adopts a higher temperature for reduction (for example, 1000 °C-1100 °C). The purpose of low temperature reduction is to reduce the metallization rate and magnetism of the ferrotitanium materials, which is beneficial to the sorting effect of the ferrotitanium materials and the chromite, and the purpose of high temperature reduction is to improve the metallization rate of the ferrotitanium materials, which is beneficial to preparing the high TiO2 grade materials. Certainly, the magnetic separation process is not merely limited to the reduction-magnetic separation process in FIG. 5 and FIG. 6, and scavenging also may be added to the magnetic separation process so as to increase the titanium recovery rate and the grade of chromium concentrate, or concentration may be added so as to improve the grade of titanium in the reduced ferrotitanium materials.
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The magnetic field in step S2 is preferably medium-low field strength for magnetic separation, and the intensity is preferably 800-4000 GS. A magnetic separator may be selected to perform dry magnetic separation or wet type magnetic separation. The wet type magnetic separation advantageously breaks the magnetic chain and the magnetic agglomeration, therefore, the sorting effect of wet type magnetic separation is superior to that of the dry magnetic separation. The process of the dry magnetic separation is simpler and also has a lower cost than the wet type magnetic separation.
The high TiO2 grade material refers to synthetic rutile or high-titanium slag having a TiO2 content greater than 75%. The synthetic rutile may be produced by an acid leaching or rusting process, and the high-titanium slag may be produced by smelting separation of the reduced ferrotitanium materials in an electric furnace, so that the deep reduction procedure for magnetic separation and sorting of the ilmenite middling is combined with the procedure of reducing ilmenite for producing the high TiO2 grade material, thereby simplifying the process of producing the high TiO2 grade material from ilmenite middling. However, different high TiO2 grade material production processes have different requirements to reducibility of ilmenite, and the reducibility of ilmenite is defined by the metallization rate (Fe/TFe) of the reduced ferrotitanium materials. Producing the synthetic rutile by the acid leaching method needs to control the metallization rate of the reduced ferrotitanium materials to be 85 %. Producing the synthetic rutile by the rusting process needs to control the metallization rate of the reduced ferrotitanium materials to be 90-95%. The production of high-titanium slag by smelting separation in electric furnace does not have a strict requirement on the metallization rate of the reduced ferrotitanium materials, but from the perspective of cost, the production cost of the high TiO2 grade materials is the lowest when the metallization rate of the reduced ferrotitanium materials is 65-85%. Specifically, steps of producing the synthetic rutile by the acid leaching method are as follows: the reduced ferrotitanium materials and a leaching acid react for 0.5-2 h at normal pressure, at a reaction temperature of 20-60 °C, wherein a mass volume ratio of the reduced ferrotitanium materials to the leaching acid is 1:(2-5), and mass fraction concentration of the leaching acid is 13-25%. Main reactions of leaching reaction of the reduced ferrotitanium materials with the leaching acid (taking sulfuric acid as an example) are as follows:
FeO+H2SO4=FeSO4+H20 Fe+H2SO4=FeSO4+H21 CaO+H2SO4=CaSO4+H20
MgO+H2SO4=MgSO4+H20
MnO+H2SO4=MnSO4+H20 A1203+3H2SO4=Al2(SO4)3+3H20
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The leaching is mainly to remove Fe, FeO, MgO, A1203, MnO, etc. from the reduced ferrotitanium materials, and to generate water-soluble sulfate impurities, a main impurity iron is converted into ferrous sulfate, and a gas generated in the reaction is hydrogen. However, TiO2 in the reduced ferrotitanium materials does not react with sulfuric acid, titanium dioxide remains in the solid phase of synthetic rutile, and the synthetic rutile is obtained after the solid-liquid separation and calcination. For hydrogen generated in the leaching reaction of ferrotitanium materials, the hydrogen may be recovered as a reducing agent for ilmenite middling or a fuel for oxidation of ilmenite middling. A leaching reaction kettle may be an atmospheric, sealed, acid-resistant reaction kettle with a stirring function. The leaching acid is preferably the waste acid from the sulfuric acid process of titanium pigment, and any one or more of other inorganic acids such as industrial hydrochloric acid, sulfuric acid, nitric acid, waste acid in titanium pigment produced by the chlorination process or other industrial waste acids, which are mixed in any proportion. Less use of hydrochloric acid and waste acid in titanium white produced by the chlorination process is recommended because the synthetic rutile prepared with hydrochloric acid is easily pulverized and affects the use. The reduced ferrotitanium materials obtained by the deep reduction are adopted, wherein the elemental iron is contained, and as the elemental iron has better activity than Fe 2 , and Fe 3 , the reaction temperature may be lower than that in the prior art (generally around 100 °C and no less than 100 °C in the prior art), and it may be completely leached out at 20-60 °C, the reduced ferrotitanium materials with a low metallization rate will also cause incomplete leaching of Fe 2+, Fe3+ at a low reaction temperature, therefore, the metallization rate of the reduced ferrotitanium materials is required to be at least 85%, and the metallization rate is preferably 85-90% taking the cost into consideration. Steps of producing the synthetic rutile by the rusting process are as follows: the reduced ferrotitanium materials and a rusting liquid react for 2-6 h under the condition of introducing air, the resultant is subjected to cyclone separation to obtain primary synthetic rutile and hydrated iron oxide, the hydrated iron oxide is dried to finally obtain iron red, wherein the reaction temperature is 30 110 °C, a mass ratio of the reduced ferrotitanium materials to the rusting liquid is 1:(2-8), the rusting liquid is an ammonium salt aqueous solution, an ammonium salt in the rusting liquid is one or a mixture of two of NH4CI and (NH4)2SO4, and ammonium salt concentration of the rusting liquid is 0.05-4 mol/L. Subsequently, the primary synthetic rutile and an inorganic acid (hydrochloric acid, sulfuric acid etc.) at mass fraction of 15-25% were added to a reaction kettle, at a liquid-to-solid ratio of 1:(3-6), and reacted at 80-100 °C for 3-5 h. Solid matters are subjected to solid-liquid separation, washing, and drying to obtain an synthetic rutile product. The rusting process is an electrochemical corrosion process performed in an electrolyte solution. Metallic iron crystallites in the particles of the reduced (28403934_1):AXG ferrotitanium materials are equivalent to anode of a galvanic cell, and outer surfaces of the particles are equivalent to cathode. At the anode, Fe loses electrons and becomes Fe2+ ions to enter the solution: Fe--Fe2++2e
In a cathode region, oxygen in the solution receives electrons to generate OH- ions:
02 +2H20+4e--*40H The dissolved Fe2+ ions in the particles diffuse along micropores into the electrolyte solution on the outer surfaces of the particles, and if the solution contains oxygen, the Fe2+ ions are further oxidized to generate iron oxide fine particle precipitation:
1 2Fe2 ++ 40H~ +-02 = Fe2 03'H20 1 +H02 2
The produced hydrated iron oxide particles are particularly fine, and according to their difference from the reduced ferrotitanium materials in physical properties (particle size and specific gravity), they can be separated from matrixes of the reduced ferrotitanium materials, and the synthetic rutile is obtained after the solid-liquid separation and calcination. The metallic iron crystallites in the reduced ilmenite particles by the rusting method are equivalent to anode of a galvanic cell to participate in reaction, therefore, the metallization rate of the reduced ferrotitanium materials is required to be higher, at least 90% or more, and in order to take the cost into consideration, the metallization rate is preferably 90-95%, and the metallization rate lower than this range is not conducive to the progress of the rusting reaction. Specific steps of producing the high-titanium slag by an electric-furnace smelting separating methods are as follows. The principle of smelting high-titanium slag by the electric furnace method is that the reduced ferrotitanium materials and the solid reducing agent (anthracite, petroleum coke or coke, etc.) are mixed according to a certain proportion (2 %) and added into an electric furnace to perform reduction smelting, a high temperature arc is generated between the electrode and furnace charge to form a molten pool (temperature is about 1600-1750 0C), and the furnace charge is heated and melted, and undergoes reduction reaction, titanium dioxide is reduced into low-valence titanium (Ti, Ti3O5, Ti2O3) in this process, and the FeO is reduced into Fe. The smelting process thereof is to smelt the reduced ferrotitanium materials at a high temperature in the electric furnace under the condition without a sufficient amount of carbon, so that the iron oxide in the reduced ferrotitanium materials is reduced into metallic iron and settled to the bottom of the furnace, while the titanium dioxide enters a slag phase together with calcium oxide, magnesium oxide, aluminum trioxide, silicon dioxide, most of manganese oxide and so on, and is finally separated from iron substances, and the titanium dioxide is enriched in the slag, thus the high-titanium slag is produced. Titanium, calcium, magnesium, aluminum, silicon, and manganese (28403934_1):AXG in the reduced ferrotitanium materials exist in a form of associated elements, calcium oxide, magnesium oxide, and aluminum trioxide do not have chemical reaction in the production process, part of titanium dioxide is converted into low valence titanium, and a trace amount of silicon dioxide and a small amount of manganese oxide are reduced into simple substances to enter molten iron. The oxide of iron in the reduced ferrotitanium materials is reduced into metallic iron, the oxide of titanium is enriched into the slag, and then a high-titanium slag and a byproduct metallic iron are obtained after separating slag and iron. Hereinafter, the present disclosure is further illustrated by taking certain titanium mineral from Mozambique as an example. Certain titanium mineral from Mozambique is a typical beach sands, with relatively coarse disseminated grain size of the mineral, complicated mineral properties, and special gangue composition, which belongs to a beach sands that are hard to separate. The raw materials used in the present disclosure are high-chromium ilmenite middling with higher chromium content, and are concentrate after conventional gravity separation and magnetic separation, with chemical composition as shown in Table 2. Table 2 Chemical Composition (%) of Certain High-chromium ilmenite middling from Mozambique
Ingredient TiO7 TFe Fe203 CaO Cr,, MgO SiO2 Al03 Mn0 V205 Sample# 38.88 35.01 50.01 0.03 5.42 0.91 1.65 1.77 0.98 0.08 Sample2# 37.321 35.95 51.358 0.025 5.634 0.78 1.87 1.79 0.95 0.09 sample3# 37.692 35.41 50.586 0.024 4.321 0.84 1.41 1.768 0.963 0.08 Sample4# 38.145 36.39 51.987 0.035 2.145 0.78 1.59 1.746 0.98 0.07 Sample# 39.79 37.34 51.51 0.04 4.43 0.94 1.47 1.76 1.02 0.09
X-ray diffraction (XRD) of certain high-chromium ilmenite middling from Mozambique in Table 2 is as shown in FIG. 1, mainly containing ilmenite (FeTiO3), hematite (Fe203), weak magnetic gangue mineral chromite ((Mg, Fe)(Cr, AI)204, MgCr204), gangue mineral quartz (SiO2), and so on. The main minerals of the high-chromium ilmenite middling are substantially consistent with the chemical ingredients of the ilmenite, and a part of the crystalline grains contain higher contents of MgO and MnO existing in an isomorphism form, and contain 51.31% of TiO2 composite sample in average. The particle size generally varies in 0.04-0.25 mm. The chromium minerals ((Mg, Fe) Cr204-(Mg, Fe) (Cr, AI)204) in the high chromium ilmenite middling, substantially in a monomeric granular form, are rarely intergrown with other minerals, have weak secondary changes, have slightly smaller grain sizes than ilmenite, generally changing in 0.04-0.2 mm, mainly manifest in that the contents of main components such as Cr203, FeO, A1203, and MgO are greatly changed, a certain amount of V205 is generally contained, wherein 47.25% of Cr203, 28.28% of FeO, 14.91% of A1203, and 0.48% of V205 are contained in average.
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Through the deep reduction, the iron (Fe 2 +, Fe 3+) in the titanium minerals and the iron minerals in the high-chromium ilmenite middling is partially or completely reduced into metallic iron (Fe) by a reducing agent, the metallic iron (FeO) in the reduced high-chromium ilmenite middling is from Fe 3+ and Fe 2+ in the titanium minerals and the iron minerals, and the magnetism of the titanium minerals and the iron minerals is increased by the metallic iron. However, iron in the weak magnetic gangue minerals chromite and garnet (iron-containing silicate minerals) is not reduced into metallic iron (FeO), the crystal lattices of the remaining non-iron-containing gangue minerals (quartz, feldspar, tourmaline, andalusite, and so on) are not changed in the reduction process, the simple substance metallic iron greatly improves the magnetism of the ferrotitanium materials and increases the magnetic difference from the weak magnetic gangue minerals, the higher the metallization rate of the reduced ferrotitanium materials is, the stronger the magnetism of the ferrotitanium materials is, and the larger the magnetic difference between the ferrotitanium materials and the gangue minerals is, the better the magnetic separation is. Through the magnetic separation, the reduced ferrotitanium materials and the tailings containing chromite are obtained, and the tailings may be further processed to obtain chromium concentrate.
FIG. 2 shows X-ray diffraction (XRD) of reduced high-chromium ilmenite middling after the deep reduction. The reduced high-chromium ilmenite middling mainly contain ilmenite (FeTiO3), rutile (TiO2), metallic iron (Fe), chromite ((Mg, Fe) (Cr, AI)204, MgCr2O4), quartz (SiO2), and so on. FIG. 3 shows X-ray diffraction (XRD) of reduced ferrotitanium materials. As can be seen from FIG. 2 and FIG. 3, X-ray diffraction characteristic peaks of metallic iron are at 44.77 °C and 65.17 °C. FIG. 4 shows X-ray diffraction (XRD) of chromium concentrate, and as can be seen from FIG. 4, no elemental iron is generated in the chromium concentrate. In the following examples, the present disclosure is further described in combination with specific examples by taking the high-chromium ilmenite middling in Table 2 as an example. Example 1 2.0 Kg of sample 1# high-chromium ilmenite middling in Table 2 and 0.35 Kg of a reducing agent coal were put in a rotary kiln, reduced at 1050 °C for 3 h, and quickly cooled to obtain reduced high-chromium ilmenite middling, with a metallization rate of 90.46%. X-ray diffraction (XRD) of the reduced high chromium ilmenite middling is as shown in FIG. 2. Dry magnetic separation was performed on the reduced high-chromium ilmenite middling at the intensity of 3000 GS to obtain reduced ferrotitanium materials containing metallic iron and magnetically separated tailings; the magnetically separated tailings were washed with water, screened, concentrated, and then dried to obtain chromium concentrate. The X-ray diffraction (XRD) of the reduced ferrotitanium materials containing metallic iron is as shown in FIG. 3. The reduced ferrotitanium materials containing metallic iron contained 0.098% of Cr203, the titanium recovery rate was 99.18% (titanium recovery rate=mass of TiO2 in the reduced ferrotitanium materials/(mass of TiO2 in the reduced ferrotitanium materials +
(28403934_1):AXG mass of TiO2 in chromite), and the chromium recovery rate in the chromite might reach 97.92%. Example 2 2.0 Kg of sample 1# high-chromium ilmenite middling in Table 2 were first put in a rotary kiln and oxidized at 750 °C for 1 h under an air atmosphere. After cooling, 0.35 Kg of a reducing agent coal was added, and the resultant was reduced at 1000 °C for 0.5 h, and quickly cooled to obtain the reduced high chromium ilmenite middling. Dry magnetic separation was performed on the reduced high-chromium ilmenite middling at the intensity of 2000 GS to obtain the ferrotitanium materials containing metallic iron and magnetically separated tailings; the magnetically separated tailings were washed with water, screened, concentrated, and then dried to obtain chromium concentrate. The reduced ferrotitanium materials containing metallic iron contained 0.052% of Cr203, the titanium recovery rate was 99.25%, and the chromium recovery rate in chromite might reach 98.93%. The iron in the ilmenite may be oxidized to generate TiO2 and Fe203. The reduction activity of Fe23 is higher than that of FeTiO3 (ilmenite), and the reduction of Fe203 is easier to control. When the activity of chromium containing ilmenite middling is lower, it may be preferable to use a method of performing oxidation first to increase the activity thereof, and then performing deep reduction. Moreover, the subsequent reduction after oxidation may adopt a lower reduction temperature or/and a shorter period of reduction. Example 3 1.0 Kg of sample 1# high-chromium ilmenite middling in Table 2 were put in a fluidized bed, with an exhaust gas of the fluidized bed containing 3.5% of H2, and reduced at 950 °C for 4 h by taking hydrogen as a reducing agent, and quickly cooled to obtain reduced high-chromium ilmenite middling. Dry magnetic separation was performed on the reduced high-chromium ilmenite middling at the intensity of 2500 GS to obtain ferrotitanium materials containing metallic iron and magnetically separated tailings; the magnetically separated tailings were washed with water, screened, concentrated, and then dried to obtain chromium concentrate. The reduced ferrotitanium materials containing metallic iron contained 0.07% of Cr203, the titanium recovery rate was 99.14%, and the chromium recovery rate in the chromite might reach 98.99%. From the above examples, it may be seen that with the method of the present disclosure, the chromium content in the reduced ferrotitanium materials can be reduced to 0.1% or less, the chromium removal rate may be up to about 99%, and meanwhile the impurity element chromium in the ilmenite is recovered to obtain chromium concentrate (chromite), thus the value of the impurity element is improved while improving the quality of the ilmenite itself. The method of the present disclosure has a simple process, a short flow sheet, and a low cost, and is easy for industrial production. Example 4
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Sample 2# ilmenite middling (Cr203 5.634%) in Table 2 were put into a rotary kiln, and reduced at 800 °C for 4 h by taking petroleum coke as a reducing agent in an addition amount of 30% of mineral amount. After quick cooling, the reduced chromium-containing ilmenite middling were subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of scavenging, at the intensity of 2500 GS, to obtain reduced ferrotitanium materials, i.e. titanium concentrate (Cr203 0.062%) and magnetically separated tailings; and the magnetically separated tailings were washed with water, screened, concentrated, and then dried to obtain chromium concentrate (Cr203 53.64%), wherein the chromium recovery rate in the chromium concentrate was 98.97%, and the titanium recovery rate in the reduced ferrotitanium materials, i.e. the titanium concentrate, was 98.35%. Example 5 Sample 3# ilmenite middling (Cr203 4.32%) in Table 2 were put in a fluidized bed, oxidized at 730 °C for 1 h under an air atmosphere, then reduced at 950 °C for 2 h by taking hydrogen as a reducing agent under the condition that an exhaust gas of the fluidized bed contained 3.5% of H2, quickly cooled, and then subjected to two times of dry magnetic separation, namely, one time of rough concentration and one time of scavenging, at the intensity of 3000 GS, to obtain reduced ferrotitanium materials, i.e. titanium concentrate (Cr203 0.07%), and tailings. The tailings were washed with water, screened, concentrated, to obtain chromium concentrate (Cr203 48.89%), wherein the chromium recovery rate in the chromium concentrate was 99.17%, and the titanium recovery rate in the reduced ferrotitanium materials, i.e. the titanium concentrate, was 98.96%. Example 6
Sample 4# ilmenite middling (Cr203 2.14%) in Table 2 were put into a rotary kiln, and reduced at 1100 °C for 0.5 h by taking coal as a reducing agent in an addition amount of 30% of mineral amount. After quick cooling, the resultants were subjected to 3 times of dry magnetic separation, namely, one time of rough concentration and two times of concentration, at the intensity of 2500 GS, to obtain reduced ferrotitanium materials, i.e. titanium concentrate (Cr203 0.057%), and tailings; and the tailings were subjected to wet magnetic separation at the intensity of 4500 GS, and dried to obtain chromium concentrate (Cr203 42.85%), wherein the chromium recovery rate in the chromium concentrate was 98.11%, and the titanium recovery rate in the reduced ferrotitanium materials, i.e. the titanium concentrate, was 99.05%. Indexes of grades and recovery rates of titanium and chromium of chromium containing ilmenite middling and chromium concentrate and reduced ferrotitanium materials, i.e. titanium concentrate having undergone the magnetic separation are as shown in Table 3. Table 3
(28403934_1):AXG itanium middling Magnetism (titanium concentrate) Chromium concentrate
Cr2O3 % Cr203 % TiO2 Yield % Cr 2O 3 % Cr 2O 3recovery rate% Example 4 5.634 0.062 98,35 53.64 98.97 Example 5 4.321 0.070 98,96 48.89 99.17 Example 6 2.145 0.057 99,05 42.85 98.11
Example 7 1 kg of sample 5# high-chromium ilmenite middling in Table 2 and 300 g of petroleum coke were put in a rotary kiln, incubated at 950 °C for 1 h, then quickly cooled to room temperature in the absence of air, and subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of concentration, at the intensity of 3000 GS to obtain reduced ferrotitanium materials and magnetically separated tailings, and the magnetically separated tailings were washed with water, screened, concentrated, and dried to obtain chromium concentrate, and the flow thereof is as shown in FIG. 5. Results are listed in Table 4. The titanium recovery rate was 99.31%, the titanium recovery rate=TiO2 mass in the reduced ferrotitanium materials/(TiO2 mass in the reduced ferrotitanium materials + TiO2 mass in chromium concentrate), and the chromium recovery rate was 98.3%. Table 4 Results of Chemical Ingredient Analysis of Product (reduced ferrotitanium materials) and Chromium Concentrate of Example 7
Wt A1 203 CaO Cr203 Fe2O3 MgO MnO SiO2 TiO2 Product
Reduced ferrotitnrunm material 89.47 0.70 0.04 0.09 50.09 0.64 1.11 1.01 42.99 Chromium Concentrate 10.53 8.72 0.27 42.40 29.41 3.02 0.49 4.97 2.53
Example 8 1 kg of sample 5# high-chromium ilmenite middling in Table 2 and 300 g of petroleum coke were put in a rotary kiln, incubated at 1100 °C for 1 h, then quickly cooled to room temperature in the absence of air, and subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of concentration, at the intensity of 3000 GS to obtain reduced ferrotitanium materials and magnetically separated tailings, and the magnetically separated tailings were washed with water, screened, concentrated, and dried to obtain chromium concentrate, and the flow thereof is as shown in FIG. 5. Results are listed in Table 5. The titanium recovery rate was 99.31%, the chromium recovery rate was 98.31%. Table 5 Results of Chemical Ingredient Analysis of Product (reduced ferrotitanium materials) and Chromium Concentrate of Example 8
(28403934_1):AXG
Wt A1203 CaO Cr203 Fe203 MgO MnO SiC 2 TiO 2 Product
Reduced terrottanium 90.53 0.902 0.062 0.078 52.142 0.454 1.026 1.209 43.441 material
Chromium 9.47 7.674 0.219 43.071 33.851 2.887 0.643 3.67 2.537 concentrate
Example 9 1 kg of sample 5# high-chromium ilmenite middling in Table 2 and 300 g of petroleum coke were put in a rotary kiln, incubated at 950 °C for 1 h, then quickly cooled to room temperature in the absence of air, and subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of concentration, at the intensity of 3000 GS to obtain magnetically separated concentrate, and then the magnetically separated concentrate and 300 g of petroleum coke were put in a rotary kiln, incubated at 1100 °C for 2 h, then quickly cooled to room temperature in the absence of air, and subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of concentration, at the intensity of 2000 GS, to obtain reduced ferrotitanium materials and magnetically separated tailings I and magnetically separated tailings 11, the magnetically separated tailings I and the magnetically separated tailings 11 were respectively washed with water, screened, concentrated, and dried to obtain chromium concentrate I and chromium concentrate 11, and the flow thereof is as shown in FIG. 6. Results are listed in Table 6. The titanium recovery rate was 99.29%, and the chromium recovery rate was 99.94%. Table 6 Results of Chemical Ingredient Analysis of Product (reduced ferrotitanium materials) and Chromium Concentrate of Example 9
Wt A203 CaO Cr203 Fe203 MgO MnO SiO2 TiO2 Product
Reduced ferrotitanium 87.37 1.05 0.15 0.06 48.47 0.63 1.07 1.45 45.04 material
Chromium concentratel 10.53 8.74 0.36 41.58 28.76 2.99 0.46 6.15 2.06
o e i ell 2.11 9.93 2.05 31.05 35.21 0.54 1.55 14.16 3.10
Example 10 1 kg of sample 5# high-chromium ilmenite middling in Table 2 and 300 g of petroleum coke were put in a rotary kiln, incubated at 1000 °C for 1 h, then quickly cooled to room temperature in the absence of air, and subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of concentration, at the intensity of 3000 GS to obtain magnetically separated concentrate, and then the magnetically separated concentrate and 300 g of petroleum coke were put in a rotary kiln, incubated at 1000 °C for 3 h, (28403934_1):AXG then quickly cooled to room temperature in the absence of air, and subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of concentration, at the intensity of 2000 GS, to obtain reduced ferrotitanium materials and magnetically separated tailings I and magnetically separated tailings 11, the magnetically separated tailings I and the magnetically separated tailings 11 were respectively washed with water, screened, concentrated, and dried to obtain chromium concentrate I and chromium concentrate 11, and the flow thereof is as shown in FIG. 6. Results are listed in Table 7. The titanium recovery rate was 99.14%, and the chromium recovery rate was 98.88%. Table 7 Results of Chemical Ingredient Analysis of Product (reduced ferrotitanium materials) and Chromium Concentrate of Example 10
Wt A1 20 3 CaO Cr203 Fe 2 0 3 MgO MnO SiO2 TiO2 Product
Reduced ferrotitanium material 87.12 0.752 0.126 0.069 48.027 0.616 1.069 1.063 45.377
concentrate 9.71 8.662 0.194 42.222 29.739 2.702 0.383 6.344 2.061 Chromium concentrate 3.17 7.391 0.623 37861 32.336 1.808 0.514 7.501 4.454
Example 11 1 kg of sample 5# high-chromium ilmenite middling in Table 2 were put in a rotary kiln, air was introduced at 950 °C for oxidization of 1 h, then nitrogen was introduced for 5 minutes, the temperature was raised to 1100 °C and CO was introduced, wherein an exhaust gas of a fluidized bed contained 3.5% of CO. the resultant was insulated for 3 h, and then quickly cooled to room temperature in the absence of air, and subjected to 2 times of dry magnetic separation, namely, one time of rough concentration and one time of concentration, at the intensity of 3000 GS to obtain reduced ferrotitanium materials and magnetically separated tailings, and the magnetically separated tailings were washed with water, sorted, and dried to obtain chromium concentrate, and the flow thereof is as shown in FIG. 5. Results are listed in Table 8. The titanium recovery rate was 99.52%, and the chromium recovery rate was 98.58%. Table 8 Results of Chemical Ingredient Analysis of Product (reduced ferrotitanium materials) and Chromium Concentrate of Example 11
Wt A1203 CaO Cr203 Fe203 MgO MnO SiO2 TiO 2 Product
Reduced ferritanium 90.32 0.73 0.11 0.07 47.37 0.87 1.13 1.11 44.91 mlateril _ _I_ ___ ___ ____ _ _
Coc ie 9.68 9.80 0.12 42.86 28.13 3.52 0.43 5.71 2.01
(28403934_1):AXG
Example 12 Raw materials of the present example are reduced ferrotitanium materials prepared under the conditions of Example 10, and results of chemical ingredient analysis thereof are listed in Table 9. The reduced ferrotitanium materials has a metallization rate of 90%. Table 9 Results of Chemical Ingredient Analysis of Raw Materials of Example 12 Ingredient Ti0 TFe Fe 0 FeO Cr 20, content % 45.38 33.62 30.26 5.19 0.07 Ingredient CaO Mg0 Si02_ A120 MnO content % 0.13 0.62 1.06 0.75 1.07
60 g of the reduced ferrotitanium materials were put in a 1000 ml beaker with a stirring function. 500 mL of waste acid from sulfuric acid pigment process at a mass fraction of 15% was added. In order to prevent reaction from being too violent and escape of hydrogen, the reduced ferrotitanium materials were slowly added in three times to the beaker with a stirring function. The temperature was controlled at about 50 °C. The whole reaction lasted for 2 h. After the reaction was ended, solid-liquid separation was performed, wherein the liquid was a ferrous sulfate solution, the solid was washed and dried to obtain a synthetic rutile product. Chemical ingredient analysis of the synthetic rutile product is shown in Table 10.
Table 10 Results of Chemical Ingredient Analysis of Synthetic Rutile of Example 12
Ingredient A1203 CaO Cr203 Fe203 MgO MnO SiO2 TiO 2
content 0.74 0.03 0.09 5.97 0.64 1.52 1.03 88.96
Example 13 Raw materials of the present example are reduced ferrotitanium materials prepared under the conditions of Example 10, and results of chemical ingredient analysis thereof are listed in Table 9. The reduced ferrotitanium materials has a metallization rate of 90%. 60 g of the reduced ferrotitanium materials were put in a 1000 ml beaker with a stirring function. 500 mL of waste acid from sulfuric acid pigment process at a mass fraction of 20% was added. In order to prevent reaction from being too violent and escape of hydrogen, the reduced ferrotitanium materials were slowly added in three times to the beaker with a stirring function. The temperature was controlled at about 50 °C. The whole reaction lasted for 1 h. After the reaction was ended, solid-liquid separation was performed, wherein the liquid was a ferrous sulfate solution, the solid was washed and dried to
(28403934_1):AXG obtain a synthetic rutile product. Chemical ingredient analysis of the synthetic rutile products is shown in Table 11. Table 11 Results of Chemical Ingredient Analysis of Synthetic Rutile of Example 13
Ingredient A1203 CaO Cr2O3 Fe203 MgO MnO SiO2 TiO2
content 0.78 0.03 0.06 5.88 0.69 1.48 1.03 89.39
Example 14 Raw materials of the present example are reduced ferrotitanium materials prepared under the conditions of Example 10, and results of chemical ingredient analysis thereof are listed in Table 9. The reduced ferrotitanium material has a metallization rate of 90%. The reduced ferrotitanium materials were added into a rusting tank, a rusting liquid was a mixed liquid of 2 mol/L ammonium chloride solution and 2 mol/L ammonium sulphate, a solid-to-liquid ratio of the solution was controlled at 1:4, air was introduced, followed by reaction at 80 0C for 2 h. The product was subjected to cyclone separation to obtain primary synthetic rutile and hydrated iron oxide, and the hydrated iron oxide was dried to finally obtain iron red; and Subsequently, the primary synthetic rutile and sulfuric acid with mass fraction of 20% were added to a reaction kettle, with a liquid-to-solid ratio of 1:4, and reacted at 80 0C for 4 h. The solid matters were subjected to solid-liquid separation, washing, and drying to obtain a synthetic rutile product. Chemical ingredient analysis of the synthetic rutile product is as shown in Table 12. Table 12 Results of Chemical Ingredient Analysis of Synthetic Rutile of Example 14
Ingredient A1203 CaO Cr203 Fe2O3 MgO MnO SiO2 TiO2
content 0.64 0.03 0.06 6.55 0.76 1.81 0.88 87.85
Example 15 Raw materials of the present example are reduced ferrotitanium materials prepared under the conditions of Example 7, and results of chemical ingredient analysis thereof are listed in Table 13. The reduced ferrotitanium material has a metallization rate of 40.13%. Table 13 Results of Chemical Ingredient Analysis of Raw Materials of Example 15
(28403934_1):AXG
Ingredient Ti02 TFe Fe 0 FeO Cr203 Content% 42.99 35.06 14.07 32.31 0.09 Ingredient CaO MgO SiO02 Al203 MnO Content % 0.04 0.64 1.01 0.70 1.11
6 kg of reduced ferrotitanium materials and 250 g of petroleum coke were mixed and added into an electric furnace, and smelted under a condition of 1650 °C. The slag/iron melt was poured into a furnace basin, and subjected to slag/iron separation after cooling. The chemical ingredient analysis of the titanium slag (titanium-rich material) product is as shown in Table 14. Table 14 Results of Chemical Ingredient Analysis of Titanium Slag (titanium rich material) of Example 15
Ingredient A120 3 CaO Cr203 Fe2O3 MgO MnO SiO 2 TiO2
content 1.49 0.14 0.14 5.73 1.34 1.52 2.06 86.69 M%)
From the above examples, it may be seen that with the method of the present disclosure, the chromium recovery rate substantially can reach about 98%, and at the same time, the chromium (Cr203) content in the titanium concentrate of the reduced ferrotitanium materials can be reduced to 0.1% or less, then the quality of the titanium concentrate itself is improved while the chromite is recovered. Meanwhile, the method of the present disclosure combines the deep reduction for purifying the ilmenite middling with the deep reduction for preparing the high TiO2 grade material from ilmenite, shortens the process route, reduces the production cost, and facilitates the industrial production. Comparative Example 1 2.0 Kg of the sample 1# high-chromium ilmenite middling in Table 2 were oxidized in a rotary kiln at 750 °C for 1 h, and the oxidized high-chromium ilmenite middling were subjected to dry magnetic separation at the intensity of 6000 GS to obtain oxidized ferrotitanium materials and tailings, wherein the oxidized ferrotitanium materials contained 0.24% of Cr203, and the titanium recovery rate was 78.53%. Comparative Example 2 2.0 Kg of the sample 1# high-chromium ilmenite middling in Table 2 were oxidized in a rotary kiln at 650 °C for 1 h, and the oxidized high-chromium ilmenite middling were subjected to dry magnetic separation at the intensity of 6000 GS to obtain oxidized ferrotitanium materials and tailings, wherein the oxidized ferrotitanium materials contained 0.35% of Cr203, and the titanium recovery rate was 79.96%.
Indexes of grades and recovery rates of titanium and chromium of chromium containing ilmenite middling and chromium concentrate/tailings (the chromium concentrate has the chromium content of 30% or more, and the tailings have (28403934_1):AXG the chromium content of less than 30%) and reduced/oxidized ferrotitanium materials, i.e. titanium concentrate after the magnetic separation are as shown in Table 15. Table 15 Results of Chemical Ingredient Analysis of Product (oxidized ferrotitanium materials) and Chromite of Comparative Examples Magnetism (titanium concentrate) (%) Chromium Concentrate (tailings)(%) Comparative Example TiO2 Cr 20 3 TiO 2 yield Mineral yield TiO 2 Cr203 Cr 2O3 recovery rate Mineral yield
Comparative Example 1 49.82 0.24 78.53 68.88 30.14 12.51 95.89 31.12 Comparative Example 2 50.48 0.35 79.96 69.60 28.97 12,83 94.07 30.40
From the above comparative examples, it may be seen that the chromium content in the titanium concentrate can hardly be reduced to 0.15% or less by removing chromium with the oxidation method, the chromium content in the titanium concentrate fails to meet the requirement, and the chromium content in the tailings is very low. Although the preferred examples of the present disclosure have been described, those skilled in the art could make additional changes and modifications to these examples once they learn the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred examples and all changes and modifications falling within the scope of the present disclosure. Obviously, those skilled in the art could make various changes and modifications to the present disclosure without departing from the spirit and scope of the present disclosure. In this way, if these modifications and variations of the present disclosure fall within the scope of the claims of the present disclosure and their equivalent technologies, the present disclosure is also intended to include these alterations and variations.
In the present specification and claims, the term 'comprising' and its derivatives including 'comprises' and 'comprise' is used to indicate the presence of the stated integers but does not preclude the presence of other unspecified integers.
Claims (11)
- Claims: 1 A method for preparing a high TiO2 grade material from ilmenite middling, the ilmenite middling comprising titanium minerals and weak magnetic gangue minerals, wherein the method comprises following steps: S1, making the ilmenite middling in contact with a reducing agent for performing deep reduction, so that Fe 2 + and/or Fe 3+ in the titanium minerals is completely or partially reduced into FeO, while Fe 2+ and/or Fe 3+ in the weak magnetic gangue minerals remain in an unreduced state, so as to obtain reduced ilmenite middling, and a temperature for the deep reduction is 800-1100 °C, and the deep reduction lasts for 0.5-4 h; S2, performing magnetic separation on the reduced ilmenite middling to obtain reduced ferrotitanium materials and tailings containing the weak magnetic gangue minerals through separation; and S3, further preparing the reduced ferrotitanium materials to obtain the high TiO2 grade material.
- 2. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 1, wherein the titanium minerals of the ilmenite middling comprise one selected from ilmenite and rutile or a combination of both, the weak magnetic gangue minerals comprise one selected from picotite, titanaugite and garnet or a combination thereof, and the ilmenite middling at least contain one titanium mineral and one weak magnetic gangue mineral.
- 3. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 1 or 2, wherein the high TiO2 grade material is synthetic rutile or high-titanium slag; and the synthetic rutile is prepared by an acid leaching or rusting process.
- 4. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 3, wherein when the high TiO2 grade material is prepared by the acid leaching method, a metallization rate of adopted reduced ferrotitanium materials is 85% or more; and when the high TiO2 grade material is prepared by the rusting process, a metallization rate of adopted reduced ferrotitanium materials is 90% or more, wherein the metallization rate is a percentage of metallic iron to total iron in the reduced ferrotitanium materials, that is, Fe/TFe x 100%.
- 5. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 4, wherein the high TiO2 grade material is prepared by the acid leaching method under a following condition that the reduced ferrotitanium materials and a leaching acid react for 0.5-2 h at normal pressure, at a reaction temperature of 20-60 °C, wherein a mass volume ratio of the reduced ferrotitanium materials to the leaching acid is 1:(2-5), and a mass fraction concentration of the leaching acid is 13-25%.
- 6. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 4, wherein the high TiO2 grade material is prepared by the rusting process under a following condition that the reduced ferrotitanium materials and a rusting liquid react for 2-6 h under a condition of introducing air, to obtain primary synthetic rutile, wherein a reaction temperature is 30-110 °C, a mass ratio of the reduced ferrotitanium materials to the rusting liquid is 1:(2-8), the rusting liquid is an ammonium salt aqueous solution, an ammonium salt in the rusting liquid is one or a mixture of two of NH4CI and (NH4)2SO4, and ammonium salt concentration of the rusting liquid is 0.05-4 mol/L; and then the primary synthetic rutile and an inorganic acid with a mass fraction of 15-25%, at a solid-to-liquid ratio of 1:(3-6), react for 3-5 h at 80-100 °C, so as to obtain the synthetic rutile.
- 7. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 3, wherein the high-titanium slag is prepared under a following condition: smelting the reduced ferrotitanium materials and a reducing agent at a smelting temperature of 1600-1750 °C.
- 8. The method for preparing a high TiO2 grade material from ilmenite middling according to any one of claims 1 to 7, wherein the reduced ferrotitanium materials obtained after the deep reduction and the magnetic separation in step S2 is further subjected to at least one time of deep reduction and magnetic separation.
- 9. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 8, wherein a temperature of the later deep reduction is not lower than that of the former deep reduction.
- 10. The method for preparing a high TiO2 grade material from ilmenite middling according to claim 9, wherein the deep reduction is performed twice, a temperature in a first deep reduction is 800-1000 °C, and a temperature in a second deep reduction is 1000-1100 °C.
- 11. A high TiO2 grade material from ilmenite middling prepared according to the method of any one of claims 1 to 10.
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| CN114293031A (en) * | 2022-01-10 | 2022-04-08 | 广东粤桥新材料科技有限公司 | Multistage-type rusting method applied to iron-containing minerals |
| CN114790517B (en) * | 2022-03-16 | 2023-10-13 | 中南大学 | Method for preparing high-quality titanium-rich material by using ilmenite |
| CN116332239B (en) * | 2023-01-10 | 2023-12-26 | 广西粤桥新材料科技有限公司 | Method for separating iron oxide red from reduced ilmenite |
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