WO1995007366A1 - Upgrading titaniferous materials - Google Patents
Upgrading titaniferous materials Download PDFInfo
- Publication number
- WO1995007366A1 WO1995007366A1 PCT/AU1994/000528 AU9400528W WO9507366A1 WO 1995007366 A1 WO1995007366 A1 WO 1995007366A1 AU 9400528 W AU9400528 W AU 9400528W WO 9507366 A1 WO9507366 A1 WO 9507366A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- leach
- caustic
- leaching
- caustic leach
- titaniferous
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000003518 caustics Substances 0.000 claims abstract description 65
- 230000008569 process Effects 0.000 claims abstract description 60
- 238000002386 leaching Methods 0.000 claims abstract description 39
- 239000012535 impurity Substances 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 18
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims description 23
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 20
- 239000002893 slag Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 12
- 239000011435 rock Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 238000004064 recycling Methods 0.000 claims 2
- 230000001172 regenerating effect Effects 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 12
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005660 chlorination reaction Methods 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052776 Thorium Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GEYMMMXKROUBAI-UHFFFAOYSA-N chlorane Chemical compound Cl.Cl.Cl.Cl.Cl GEYMMMXKROUBAI-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1254—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using basic solutions or liquors
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention relates to the removal of impurities from naturally occurring and synthetic titaniferous materials.
- the invention is particularly suited to the enhancement of titaniferous materials used in the production of titanium metal and titanium dioxide pigments by means of industrial chlorination systems.
- Embodiments of the present invention have the common features of the use of caustic leaching and pressure sulphuric acid leaching for the upgrading of titaniferous materials, e.g. titaniferous slags, derived from hard rock ilmenites. Additional steps may be employed as will be described below.
- titanium dioxide bearing feedstocks are fed with coke to chlorinators of various designs (fluidised bed, shaft, molten salt), operated to a maximum temperature in the range 700 - 1200°C.
- chlorinators of various designs (fluidised bed, shaft, molten salt), operated to a maximum temperature in the range 700 - 1200°C.
- the most common type of industrial chlorinator is of the fluidised bed design.
- Gaseous chlorine is passed through the titania and carbon bearing charge, converting titanium dioxide to titanium tetrachloride gas, which is then removed in the exit gas stream and condensed to liquid titanium tetrachloride for further purification and processing.
- the chlorination process as conducted in industrial chlorinators is well suited to the conversion of pure titanium dioxide feedstocks to titanium tetrachloride.
- most other inputs i.e. impurities in feedstocks
- the attached table provides an indication of the types of problems encountered.
- each unit of inputs which does not enter products contributes substantially to the generation of wastes for treatment and disposal.
- Some inputs e.g. particular metals, radioactives
- Preferred inputs to chlorination are therefore high grade materials, with the mineral rutile (at 95-96% Ti0 2 ) the most suitable of present feeds. Shortages of rutile have led to the development of other feedstocks formed by upgrading naturally occurring ilmenite (at 40-60% Ti0 2 ), such as titaniferous slag (approximately 86% Ti0 2 ) and synthetic rutile (variously 92-95% Ti0 2 ) . These upgrading processes have had iron removal as a primary focus, but have extended to removal of magnesium, manganese and alkali earth impurities, as well as some aluminium.
- Si Accumulates Can May require i ne ncourage distillat ion chlorinator, d u c t from product r e d u c i n gb lockage . c a m p a i g n Condenses in life. part with
- titaniferous minerals e.g. ilmenite
- the titaniferous mineral is reduced with coal or char in a rotary kiln, at temperatures in excess of 1100°C.
- the iron content of the mineral is substantially metallised.
- Sulphur additions are also made to convert manganese impurities partially to sulphides.
- the metallised product is cooled, separated from associated char, and then subjected to aqueous aeration for removal of virtually all contained metallic iron as a separable fine iron oxide.
- the titaniferous product of separation is treated with 2-5% aqueous sulphuric acid for dissolution of manganese and some residual iron.
- aqueous sulphuric acid for dissolution of manganese and some residual iron.
- Recent disclosures have provided a process which operates reduction at lower temperatures and provides for hydrochloric acid leaching after the aqueous aeration and iron oxide separation steps. According to these disclosures the process is effective in removing iron, manganese, alkali and alkaline earth impurities, a substantial proportion of aluminium inputs and some vanadium as well as thorium.
- the process may be operated as a retrofit on existing kiln based installations. However, the process is ineffective in full vanadium removal and has little chemical impact on silicon.
- ilmenite is first thermally reduced to substantially complete reduction of its ferric oxide content (i.e. without substantial metallisation), normally in a rotary kiln.
- the cooled, reduced product is then leached under 35 psi pressure at 140-150°C with excess 20% hydrochloric acid for removal of iron, magnesium, aluminium and manganese.
- the leach liquors are spray roasted for regeneration of hydrogen chloride, which is recirculated to the leaching step.
- the ilmenite undergoes grain refinement by thermal oxidation followed by thermal reduction (either in a fluidised bed or a rotary kiln) .
- the cooled, reduced product is then subjected to atmospheric leaching with excess 20% hydrochloric acid, for removal of the deleterious impurities. Acid regeneration is also performed by spray roasting in this process.
- ilmenite is thermally reduced (without metallisation) with carbon in a rotary kiln, followed by cooling in a non-oxidising atmosphere.
- the cooled, reduced product is leached under 20 - 30 psi gauge pressure at 130°C with 10 - 60% (typically 18 - 25%) sulphuric acid, in the presence of a seed material which assists hydrolysis of dissolved titania, and consequently assists leaching of impurities.
- Hydrochloric acid usage in place of sulphuric acid has been claimed for this process. Under such circumstances similar impurity removal to that achieved with other hydrochloric acid based systems is to be expected. Where sulphuric acid is used radioactivity removal will not be complete.
- a commonly adopted method for upgrading of ilmenite to higher grade products is to smelt ilmenite at temperatures in excess of 1500°C with coke addition in an electric furnace, producing a molten titaniferous slag (for casting and crushing) and a pig iron product.
- molten titaniferous slag for casting and crushing
- pig iron product Of the problem impurities only iron is removed in this manner, and then only incompletely as a result of compositional limitations of the process.
- a titaniferous ore is treated by alternate leaching with an aqueous solution of alkali metal compound and an aqueous solution of a non-sulphuric mineral acid (US Patent No. 5,085,837).
- the process is specifically limited to ores and concentrates and does not contemplate prior processing aimed at artificially altering phase structures. Consequently the process requires the application of excessive reagent and harsh processing conditions to be even partially effective and is unlikely to be economically implemented to produce a feedstock for the chloride pigment process.
- a wide range of potential feedstocks is available for upgrading to high titania content materials suited to chlorination.
- Examples of primary titania sources which cannot be satisfactorily upgraded by prior art processes for the purposes of production of a material suited to chlorination include hard rock (non detrital) ilmenites, siliceous leucoxenes, many primary (unweathered) ilmenites and large anatase resources.
- Many such secondary sources e.g. titania bearing slags also exist.
- titania reserves A large portion of the world's identified titania reserves is in the form of hard rock ilmenites.
- the residue of the caustic leach was subjected to a leach with refluxing 20% hydrochloric acid at 30% slurry density for 6 hours. After filtration and washing the solid residue had the composition which is also indicated in Table 2.
- Example 1 The treatment indicated in Example 1 was repeated with the exception that the caustic leach was conducted under pressure at 165°C.
- the residue of the caustic leach was subjected to a pressure leach at 150°C with 20% sulphuric acid at 5% slurry density for 6 hours. After filtration and washing the solid residue had the composition which is also indicated in Table 4.
- titaniferous slag having the composition shown in Table 1 was subjected to roasting for two hours in an atmosphere of 1:19 (volumetric basis) of hydrogen to carbon dioxide at 1000°C. After cooling in the roasting atmosphere the roasted slag was pressure leached at 135°C in 20% sulphuric acid at 25% w/w slurry density for six hours.
- Example 5 A sample of slag to which no addition of additive had been made and which was not subjected to any thermal treatment was treated by the same leaching steps as indicated in Example 3.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU76475/94A AU697952B2 (en) | 1993-09-07 | 1994-09-07 | Upgrading titaniferous materials |
JP7508358A JPH09504828A (en) | 1993-09-07 | 1994-09-07 | Improving the quality of titanium-containing raw materials |
EP94926722A EP0717783A4 (en) | 1993-09-07 | 1994-09-07 | Upgrading titaniferous materials |
NO19960917A NO317932B1 (en) | 1993-09-07 | 1996-03-06 | Quality improvement of titanium-containing materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPM1051 | 1993-09-07 | ||
AUPM105193 | 1993-09-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995007366A1 true WO1995007366A1 (en) | 1995-03-16 |
Family
ID=3777178
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU1994/000528 WO1995007366A1 (en) | 1993-09-07 | 1994-09-07 | Upgrading titaniferous materials |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0717783A4 (en) |
JP (1) | JPH09504828A (en) |
CN (1) | CN1042349C (en) |
CA (1) | CA2171185A1 (en) |
NO (1) | NO317932B1 (en) |
WO (1) | WO1995007366A1 (en) |
ZA (1) | ZA946864B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995028502A1 (en) * | 1994-04-15 | 1995-10-26 | Technological Resources Pty. Ltd. | Leaching of a titaniferous material |
WO1995028503A1 (en) * | 1994-04-15 | 1995-10-26 | Technological Resources Pty Ltd | Treatment of leach liquors for upgrading a titaniferous material |
US6627165B2 (en) * | 1994-04-15 | 2003-09-30 | Technological Resources Pty Ltd | Process for upgrading a titaniferous material containing silica |
WO2005024074A1 (en) * | 2003-09-05 | 2005-03-17 | Promet Engineers Pty Ltd | Process for extracting crystalline titanium oxides |
RU2336348C1 (en) * | 2007-03-07 | 2008-10-20 | Николай Васильевич Туляков | Method of processing titanium-silicon containing concentrates with production of artificial rutile |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1060817C (en) * | 1997-08-08 | 2001-01-17 | 杨道光 | Electrolytic separating process for ilmenite |
RU2264478C1 (en) * | 2004-05-26 | 2005-11-20 | Федун Марина Петровна | Method of processing of titanium-silicon containing concentrates |
WO2007052801A1 (en) * | 2005-11-07 | 2007-05-10 | Tohoku University | Method for extraction of rutile |
RU2377332C2 (en) * | 2008-02-19 | 2009-12-27 | Государственное образовательное учреждение высшего профессионального образования Томский политехнический университет | Method to process titanium-silicon-containing stock |
RU2390572C1 (en) * | 2008-11-19 | 2010-05-27 | ООО "Гирмет" | Method of processing quartz-leucoxene concentrates |
CN103834798B (en) * | 2012-11-26 | 2015-11-18 | 贵阳铝镁设计研究院有限公司 | By low-grade TiO 2slag prepares the method for rich titanium material |
CN103966423B (en) * | 2014-04-23 | 2016-02-03 | 鞍钢集团矿业公司 | Alkali leaching, pickling and gravity treatment is utilized to select the method for v-ti magnetite concentrate again |
CN103952533B (en) * | 2014-04-23 | 2016-01-20 | 鞍钢集团矿业公司 | Calcining, alkali leaching and desliming is utilized to select the method for v-ti magnetite concentrate again |
RU2592655C2 (en) * | 2014-12-24 | 2016-07-27 | Федеральное государственное бюджетное учреждение науки Объединенный институт высоких температур Российской академии наук (ОИВТ РАН) | Method of thermochemical processing of rare metal raw material |
CN104828864B (en) * | 2015-05-26 | 2017-07-21 | 昆明冶金研究院 | The technique that a kind of ilmenite salt Ore Leaching prepares synthetic rutile |
RU2623564C1 (en) * | 2016-04-25 | 2017-06-27 | Федеральное государственное бюджетное учреждение науки Институт металлургии и материаловедения им. А.А. Байкова Российской академии наук (ИМЕТ РАН) | Method of processing leukoxene concentrate |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021533A (en) * | 1974-10-04 | 1977-05-03 | Societa' Italiana Resine S.I.R. S.P.A. | Manufacture of titanium dioxide by the sulphate process using nuclei formed by steam hydrolysis of TiCl4 |
AU3403478A (en) * | 1977-03-09 | 1979-09-13 | Mineracao Vale Do Paranaiba S.A.-Valep | Obtaining higher grade anatase concentrate from lower grade anatase concentrate |
US4176159A (en) * | 1976-11-15 | 1979-11-27 | Mendonca Paulo Ayres Falcao De | Process for concentration of titanium containing anatase ore |
AU3900289A (en) * | 1988-07-28 | 1990-02-01 | E.I. Du Pont De Nemours And Company | Method for purifying tio2 ore |
AU5316590A (en) * | 1989-04-17 | 1990-10-18 | Bayer Aktiengesellschaft | A process for the production of titanium dioxide |
AU1498192A (en) * | 1991-04-19 | 1992-10-22 | Rgc Mineral Sands Limited | Removal of radionuclides from titaniferous material |
AU1498092A (en) * | 1991-04-19 | 1992-10-22 | Rgc Mineral Sands Limited | Removal of radionuclides from titaniferous material |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE276025C (en) * | ||||
GB711833A (en) * | 1949-03-03 | 1954-07-14 | Nat Titanium Pigments Ltd | Improved manufacture of titanium compounds |
JPH01301518A (en) * | 1988-05-28 | 1989-12-05 | Sakai Chem Ind Co Ltd | Production of titanium dioxide |
BR9106105A (en) * | 1990-03-02 | 1993-02-24 | Wimmera Ind Minerals Pty Ltd | PROCESS TO BENEFIT THE TITANIA CONTENT OF A MINING OR TITANIFER CONCENTRATE |
US5063032A (en) * | 1990-03-27 | 1991-11-05 | Qit-Fer Et Titane, Inc. | Method of preparing a synthetic rutile from a titaniferous slag containing magnesium values |
-
1994
- 1994-09-07 ZA ZA946864A patent/ZA946864B/en unknown
- 1994-09-07 CA CA002171185A patent/CA2171185A1/en not_active Abandoned
- 1994-09-07 WO PCT/AU1994/000528 patent/WO1995007366A1/en not_active Application Discontinuation
- 1994-09-07 JP JP7508358A patent/JPH09504828A/en active Pending
- 1994-09-07 EP EP94926722A patent/EP0717783A4/en not_active Withdrawn
- 1994-09-07 CN CN94194061A patent/CN1042349C/en not_active Expired - Fee Related
-
1996
- 1996-03-06 NO NO19960917A patent/NO317932B1/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021533A (en) * | 1974-10-04 | 1977-05-03 | Societa' Italiana Resine S.I.R. S.P.A. | Manufacture of titanium dioxide by the sulphate process using nuclei formed by steam hydrolysis of TiCl4 |
US4176159A (en) * | 1976-11-15 | 1979-11-27 | Mendonca Paulo Ayres Falcao De | Process for concentration of titanium containing anatase ore |
AU3403478A (en) * | 1977-03-09 | 1979-09-13 | Mineracao Vale Do Paranaiba S.A.-Valep | Obtaining higher grade anatase concentrate from lower grade anatase concentrate |
AU3900289A (en) * | 1988-07-28 | 1990-02-01 | E.I. Du Pont De Nemours And Company | Method for purifying tio2 ore |
AU5316590A (en) * | 1989-04-17 | 1990-10-18 | Bayer Aktiengesellschaft | A process for the production of titanium dioxide |
AU1498192A (en) * | 1991-04-19 | 1992-10-22 | Rgc Mineral Sands Limited | Removal of radionuclides from titaniferous material |
AU1498092A (en) * | 1991-04-19 | 1992-10-22 | Rgc Mineral Sands Limited | Removal of radionuclides from titaniferous material |
Non-Patent Citations (4)
Title |
---|
DERWENT ABSTRACT; Accession No. 84-181664/29, Class E32; & SU,A,1 054 296 (KHAKONOV), 15 November 1983 (15.11.83). * |
Derwent Soviet Inventions Illustrated, Section 1, Chemical, issued November 1969, General Inorganic, p. 3; & SU,A,235 883 (BORODINA et al.), 12 June 1969 (12.06.69). * |
PATENT ABSTRACTS OF JAPAN, C-17, page 691; & JP,A,1 301 518 (SAKAI CHEM IND CO LTD), 5 December 1989 (05.12.89). * |
See also references of EP0717783A4 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995028502A1 (en) * | 1994-04-15 | 1995-10-26 | Technological Resources Pty. Ltd. | Leaching of a titaniferous material |
WO1995028503A1 (en) * | 1994-04-15 | 1995-10-26 | Technological Resources Pty Ltd | Treatment of leach liquors for upgrading a titaniferous material |
US5885536A (en) * | 1994-04-15 | 1999-03-23 | Technological Resources Pty Ltd | Process for alkaline leaching a titaniferous material |
US6627165B2 (en) * | 1994-04-15 | 2003-09-30 | Technological Resources Pty Ltd | Process for upgrading a titaniferous material containing silica |
WO2005024074A1 (en) * | 2003-09-05 | 2005-03-17 | Promet Engineers Pty Ltd | Process for extracting crystalline titanium oxides |
RU2336348C1 (en) * | 2007-03-07 | 2008-10-20 | Николай Васильевич Туляков | Method of processing titanium-silicon containing concentrates with production of artificial rutile |
Also Published As
Publication number | Publication date |
---|---|
NO960917L (en) | 1996-04-25 |
NO317932B1 (en) | 2005-01-10 |
EP0717783A1 (en) | 1996-06-26 |
ZA946864B (en) | 1995-09-04 |
NO960917D0 (en) | 1996-03-06 |
EP0717783A4 (en) | 1997-04-23 |
CA2171185A1 (en) | 1995-03-16 |
CN1042349C (en) | 1999-03-03 |
CN1134730A (en) | 1996-10-30 |
JPH09504828A (en) | 1997-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8834600B2 (en) | Extraction process for reactive metal oxides | |
US6500396B1 (en) | Separation of titanium halides from aqueous solutions | |
US5885536A (en) | Process for alkaline leaching a titaniferous material | |
JP5171631B2 (en) | Beneficiation of titanium ore | |
WO1995007366A1 (en) | Upgrading titaniferous materials | |
US20020104406A1 (en) | Upgrading titaniferous materials | |
US5730774A (en) | Process for upgrading titaniferous materials | |
US7494631B2 (en) | Titaniferous ore beneficiation | |
AU749393C (en) | Beneficiation of titania slag by oxidation and reduction treatment | |
EP0755459A1 (en) | Leaching of a titaniferous material | |
US6627165B2 (en) | Process for upgrading a titaniferous material containing silica | |
CN113957271B (en) | Method for reducing calcium oxide content in titanium slag and titanium dioxide | |
AU700536B2 (en) | Leaching of a titaniferous material | |
AU697952B2 (en) | Upgrading titaniferous materials | |
AU678375C (en) | Upgrading titaniferous materials | |
AU1005802A (en) | Upgrading titaniferous materials | |
CA2137812C (en) | Upgrading titaniferous materials | |
AU690977B2 (en) | Treatment of leach liquors for upgrading a titaniferous material | |
AU2387799A (en) | Upgrading titaniferous materials | |
Mukherjee et al. | Status of Waste Treatment in Titanium Mineral Industries | |
AU2008201905A1 (en) | Upgrading titaniferous materials | |
AU687054B2 (en) | Process for upgrading titaniferous materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 94194061.6 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU JP KE KG KP KR KZ LK LR LT LU LV MD MG MN MW NL NO NZ PL PT RO RU SD SE SI SK TJ TT UA US UZ VN |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): KE MW SD AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2171185 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1994926722 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1994926722 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1994926722 Country of ref document: EP |