WO2005028369A1 - Process for the recovery of titanium dioxide from titanium-containing compositions - Google Patents
Process for the recovery of titanium dioxide from titanium-containing compositions Download PDFInfo
- Publication number
- WO2005028369A1 WO2005028369A1 PCT/GB2004/003925 GB2004003925W WO2005028369A1 WO 2005028369 A1 WO2005028369 A1 WO 2005028369A1 GB 2004003925 W GB2004003925 W GB 2004003925W WO 2005028369 A1 WO2005028369 A1 WO 2005028369A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- titanium oxide
- containing material
- group
- alumina
- alkali
- Prior art date
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 61
- 229910052719 titanium Inorganic materials 0.000 title claims description 7
- 239000010936 titanium Substances 0.000 title claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 5
- 239000004408 titanium dioxide Substances 0.000 title claims description 5
- 238000011084 recovery Methods 0.000 title description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002386 leaching Methods 0.000 claims abstract description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000292 calcium oxide Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 25
- 150000001447 alkali salts Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 7
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- -1 K2SO Chemical compound 0.000 claims description 5
- 150000004679 hydroxides Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910001388 sodium aluminate Inorganic materials 0.000 claims 1
- 230000002285 radioactive effect Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 229910052747 lanthanoid Inorganic materials 0.000 description 10
- 150000002602 lanthanoids Chemical class 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 239000010955 niobium Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910052768 actinide Inorganic materials 0.000 description 8
- 150000001255 actinides Chemical class 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 229910052776 Thorium Inorganic materials 0.000 description 7
- 229910052770 Uranium Inorganic materials 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- 235000013980 iron oxide Nutrition 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910052845 zircon Inorganic materials 0.000 description 6
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 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 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical group 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052590 monazite Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009852 extractive metallurgy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- 229910017144 Fe—Si—O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910008005 Si-M-O Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000005324 oxide salts Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—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
- C22B34/1259—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 treatment or purification of titanium containing solutions or liquors or slurries
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- the present invention relates to a process for recovering titanium dioxide from a titanium oxide-containing composition such as an ore.
- a titanium oxide-containing composition such as an ore.
- Existing supplies of ilmenite and natural rutile are coming under pressure due to a steady growth in TiO 2 markets and a rise in demand for high-grade ores for direct chlorination or for the production of synthetic rutile.
- the new beach sand/placer deposits are of variable quality and many are unsuitable for upgrading and beneficiation using existing commercial processes (Nameny 'Challenges and Opportunities in the TiO ⁇ Feedstock Industry ', AJM Global Mineral Sands Exploration and Investment Conference, Melbourne, 2003).
- Most TiO 2 -ores have high concentrations of zircon and monazite minerals due to their geological proximity.
- the zircon and monazite impurities in the feedstock reduce its market value.
- Actinide and lanthanide impurities create operational problems (eg high chlorine consumption or sticky beds) and generate hazardous waste with high concentrations of actinides, lanthanides and other heavy metals. Due to stringent environmental regulations in many countries, the treatment and disposal of such hazardous waste from pigment industries has become a major problem which is increasing the cost of waste treatment and management.
- Conventional processes for beneficiation of TiO ores are a) physical processes such as gravitational, magnetic and electrical separation which are used to separate the magnetite, monazite, zircon and other siliceous gangue and b) chemical processes, namely acid leaching and TiO 2 -slag formation (high temperature reduction) which are mainly used to remove iron (Becher, Benilite, Austpac).
- the slagging process (which is the main source of feedstock for pigment manufacturing) separates only iron oxides and most of the other impurities enter the feedstock eg in the TiO 2 -slags.
- the slagging process is also facing uncertainty due to its high power consumption and emission of greenhouse gas.
- There have been a number of investigations into the roasting of ilmenite with soda, mainly in a reducing atmosphere with carbon ed Fathi Habashi, Handbook of Extractive Metallurgy, Vol. II, PubL: Wiley-NCH, Berlin, 1997).
- the yield of TiO 2 in this technique is not very high ( ⁇ 90wt%).
- the major drawback of this process is that neither is iron separated in the metallic form nor is a leachable product produced (Handbook of Extractive Metallurgy [supra]).
- a limited number of investigations have been carried out on oxidative alkali roasting techniques.
- the yield of TiO 2 and separation out of actinides and lanthanides is below the required levels for chlorination (US-A-6346223).
- the present invention seeks to improve beneficiation of a titanium oxide-containing composition (such as a low-grade or highly radioactive TiO 2 ore) by combining roasting and selective leaching steps.
- the present invention relates to a beneficiation process for separation of non-lanthanide (eg Fe, Ca, Si, V and Cr), pre-lanthanide (eg Zr and ⁇ b), lanthanide (eg Ce and ⁇ d) and actinide (eg U and Th) impurities from titaniferrous deposits.
- non-lanthanide eg Fe, Ca, Si, V and Cr
- pre-lanthanide eg Zr and ⁇ b
- lanthanide eg Ce and ⁇ d
- actinide eg U and Th
- the process of the invention may successfully upgrade a wide range of titanium oxide-containing compositions and produce a high purity titanium oxide product (preferably synthetic rutile) for direct use in pigment production (chlorination and sulphatation).
- a high purity titanium oxide product preferably synthetic rutile
- the process of the invention may achieve a complete, efficient and economical separation out of large concentrations of iron oxides and lanthanide and actinide impurities which otherwise contribute to the feedstock in pigment production.
- alumina-containing material or a calcium oxide-containing material helps to remove not only zircon and monazite minerals but also lanthanide and actinide impurities (solute) present in the lattice of the TiO 2 phases (rutile, pseudorutile, brookite, etc).
- the process also recovers metal values as value-added byproducts and alkali salts thereby substantially reducing the amount of waste and usage of raw materials (namely alkali salt and alumina) which can be recycled to make the process economically viable.
- titanium oxide-containing compositio ' ' is meant a mixture of metal oxide species in compound form or forms which include titania (TiO 2 ).
- the titanium oxide- containing composition may be synthetic or (preferably) natural such as a powder, ore or mineral or a mixture thereof.
- a titanium rich material such as an ore (eg ilmenite, anatase, ilmenite beach sands, low grade titaniferrous slag, natural rutile or perovskite).
- titaniferrous mixtures which further include at least one iron species such as a ferrous or ferric species (preferably an iron oxide such as FeO, Fe 2 O 3 or Fe 3 O 4 ).
- the titaniferrous mixture may further comprise alumina or silica.
- the titanium oxide-containing composition may be a residue from a chlorination or sulphatation process.
- the mineral ores are selected from the group consisting of ilmenite, anatase and perovskite.
- the mineral ore is a mixture of ilmenite and perovskite.
- the one or more alkali salts is one or more alkali metal or alkaline earth metal salts.
- the one or more alkali salts is one or more carbonates, hydroxides, bicarbonates or sulphates of a group IA or group IIA metal or a mixture thereof.
- the one or more alkali salts may be selected from the group consisting of Na 2 CO 3 , K 2 CO 3 , Na 2 SO 4 , K 2 SO 4 , NaOH, NaHSO 4 , KHSO 4 , KHCO 3 , NaHCO 3 and KOH.
- Sodium and/or potassium carbonate are preferred.
- the amount of alkali salt may be calculated based on the formation of alkali compounds of TiO 2 , Fe 2 O 3 , Al 2 O 3 , SiO 2 , and P 2 O 5 present in the composition (eg ore).
- step (a) comprises: providing the titanium oxide-containing composition with one or more alkali salts and with an alumina-containing material and a calcium oxide-containing material.
- Step (b) may be carried out at a temperature in the range 500°C to 1000°C, preferably 700°C to 975°C, more preferably 700°C to 875°C (eg about 800°C) in air or another source of oxygen.
- Step (b) may be carried out in a conventional rotary kiln or a rotary hearth furnace.
- Step (b) may be carried out for a suitable length of time (eg 120 minutes).
- Step (b) generally forms alkali titanates and complex oxide salts.
- Step (a) typically includes mixing (eg homogeneously mixing) the titanium oxide- containing composition with one or more alkali salts and with at least one of the alumina- containing material and the calcium oxide-containing material to produce the charge.
- the alumina-containing material or calcium oxide-containing material may undergo controlled addition to the titanium oxide-containing composition.
- the alumina-containing material eg alumina
- the alumina-containing material is present in the charge in an amount in the range 5 to 30wt% of the titanium oxide-containing composition, preferably 10 to 25wt% of the titanium oxide-containing composition, more preferably 15 to 22wt% (eg about 20wt%) of the titanium oxide-containing composition.
- the precise amount of alumina-containing materials in the charge generally depends on the ratio of titanium oxide-containing compositio alkali salt, formation of liquid phase and the concentration of various impurities (mainly iron oxides, silicates and phosphates).
- the alumina-containing material may be alumina, aluminum hydroxide, Al 2 O -containing clay or a mixture thereof.
- An aluminate (egNaAlO 2 ) may also be used.
- alumina along with other gangue phases in the titanium oxide-containing composition react with the alkali salt and form complex oxide phases (such as Na-Al-Si-M-O phases) which increase the solubility and stability of ferrites such as sodium ferrite.
- This complex salt phase thereby helps to separate out iron oxides from the titanium oxide-containing composition.
- the calcium oxide-containing material may be lime (ie CaO or Ca(OH) 2 ), calcium oxide (eg calcite) or a mixture thereof.
- the calcium oxide-containing material (eg CaO) is present in the charge in an amount in the range 0.1 to 5wt% of the titanium oxide-containing composition, preferably 1 to 4wt% of the titanium oxide-containing composition, more preferably 2 to 3wt% of the titanium oxide-containing composition.
- the addition of the calcium oxide-containing material is on the basis of the formation of perovskite and pyrochlore-type phases of TiO 2 and ZrO 2 which can dissolve high concentrations of inter alia rare earth elements REEs (eg U or Th) and Nb (De Hoog et al, Mineralogical Magazine, 61, 721-725, 1997).
- CaO reacts with TiO 2 and zircon minerals and forms various Ca-Na-Ti-M-O compounds such as perovskite (CaTiO 3 ), zirconolite [(Ca,Fe,Y,Th) 2 (Fe,Ti,Nb) 3 Zr 2 O 7 ] and hiarneite [(Ca,Mn,Na) 2 (Zr,Mn) 5 (Sb,Ti,Fe) 2 O 16 ] which advantageously absorb most of the lanthanide and actinide impurities in the monazite and zircon minerals.
- perovskite CaTiO 3
- zirconolite (Ca,Fe,Y,Th) 2 (Fe,Ti,Nb) 3 Zr 2 O 7 ]
- hiarneite [(Ca,Mn,Na) 2 (Zr,Mn) 5 (Sb,Ti,Fe) 2 O 16 ] which advantageously absorb most of the lan
- Step (c) may comprise: (cl) adding to the roasted mass an aqueous medium to produce an aqueous solution and a substantially insoluble residue.
- the aqueous medium may be water or an alkali solution (eg a dilute alkali solution). Typically water is used at an elevated temperature.
- the hot water may be at a temperature in the range 70 to 90°C.
- Step (cl) may be carried out in hot water for 20 to 200 minutes, preferably 25 to 100 minutes (eg 40 minutes).
- water-soluble alkali compounds such as metal (eg sodium) aluminate, silicate, chromate, vanadate and phosphate may be dissolved in the aqueous solution.
- Aqueous medium may be added repeatedly to wash the substantially insoluble residue (typically until the pH of the washings reaches about 7).
- step (cl) comprises: (cla) adding water at an elevated temperature to the roasted mass to produce an aqueous solution and a substantially insoluble residue;
- the fine precipitate generally comprises fine particles of titanium oxide-containing composition (eg ore) and constituents of complex alkali salts (eg Na-Al-Si-Fe-M-O) which precipitate as oxides or hydroxides of Fe, Nb, Al or RREs (eg U and Th) due to their limited solubility.
- the fine precipitate may be separated from the aqueous solution by standard techniques such as filtration.
- the source of alkalinity is preferably an ammonium salt such as a carbonate, sulphate, bisulphate or bicarbonate. Typically the ammonium salt is added in an amount up to 5wt% to optimize precipitation kinetics.
- the process further comprises: (d) recovering metal values from the fine precipitate.
- the metal values may be selected from the group consisting of alumina- containing material (eg alumina), calcium oxide-containing material (eg CaO) and metal oxides (eg iron oxide such as Fe 2 O 3 or niobium oxide such as Nb 2 O 5 ).
- the process further comprises: (e) recovering metal values from the aqueous solution.
- the metal values may be selected from the group consisting of alkali salt, alumina-containing material (eg alumina), calcium oxide-containing material (eg CaO) V 2 O 5 , Fe 2 O 3 and Cr 2 O 3 .
- step (e) comprises: (el) acidifying the aqueous solution.
- Step (el) may be performed by the addition of a weak acid.
- the acid is an inorganic acid (eg an inorganic acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, nitric acid, sulphuric acid, an acidic oxide and mixtures thereof).
- Step (el) may be better controlled by using a weak organic acid such as formic, oxalic or acetic acid and/or CO 2 .
- the acid is an acidic oxide, particularly preferably carbon dioxide.
- step (el) may include: bubbling CO 2 gas through (or passing oxalic acid into) the aqueous solution.
- the addition of weak acid and/or CO 2 provides precise control of pH for selective precipitation of oxides.
- the use of an acid with CO 2 also helps precipitation coarsening kinetics and therefore reduces the entrapment of small particles of impurity oxides with coarser TiO 2 -rich particles in the coarse residue.
- Step (c) of the process preferably further comprises: (c2) acid leaching the substantially insoluble residue to produce an acid leachate and a solid residue consisting essentially of titanium oxide.
- Step (c2) may be carried out in an acid solution, preferably an inorganic acid solution (such as a 2-10% mineral acid (eg HC1, HNO 3 or H 2 SO 4 ) solution).
- An example of a suitable acid is 5% HC1.
- the acid is at an elevated temperature (eg 70- 90°C).
- Step (c2) may be carried out for 5 to 200 minutes, preferably 5 to 100 minutes (eg 10 minutes).
- the concentration of acid and solid-to-liquid ratio are generally based on the amount of insoluble salts of Fe 2 O 3 , SiO 2 and CaO compounds in the substantially insoluble residue from step (cl).
- the solid residue may be separated from the acid leachate by standard techniques such as filtration.
- acid-soluble salts of inter alia Nb, Zr and REEs eg U and Th
- Alkali titanates are decomposed to TiO 2 .
- Dilute acid and optionally then water
- step (c2) comprises: (c2a) recovering metal values from the acid leachate.
- the metal values may be selected from the group consisting of acidic compounds, alkali compounds and oxides. Specific examples are ZrO 2 , Nb 2 Os and Th/UO 2 .
- the solid residue after step (c2) is TiO 2 -rich and may comprise 87wt% or more of TiO 2 (dependent upon the fineness of oxides produced in step (el)), preferably 87-95wt%. Further purification of the solid residue may be carried out (eg by electrolytic purification techniques or calcining).
- Calcining may be carried out using alkali bisulphates and bicarbonates to further reduce levels of iron, aluminium, silica, phosphate, lanthanide and actinide to produce whiter grades of synthetic rutile. Purification and agglomeration of the solid residue may form synthetic rutile with a desired level of purity and particle size distribution.
- step (c) of the process further comprises: (c3) roasting at least a proportion of the solid residue with one or more alkali hydrogen sulphates and/or carbonates to produce a roast.
- step (c3) is carried out at low temperature such as 200-400°C (eg at about 300°C) in air or another source of oxygen for 1 to 4 hours.
- Preferred alkali hydrogen sulphates are NaHSO 4 and/or KHSO 4 .
- the ratio of NaHSO 4 or KHSO 4 to solid residue is about 1 :1.
- step (c3) is carried out for 1 hour.
- Step (c) of the process preferably further comprises: (c4) water leaching the roast to produce the titanium oxide product.
- water is used in step (c4) at an elevated temperature.
- the hot water may be at a temperature in the range 70 to 90°C.
- Step (c4) may be carried out in hot water for 20 to 200 minutes, preferably 25 to 100 minutes (eg 30 minutes).
- the titanium oxide product may be separated from the water leachate by standard techniques such as filtration. Water and optionally dilute acid solution may be added repeatedly to wash the roast (typically until the pH of the washings reaches about 7).
- the titanium oxide product is preferably in the form of synthetic rutile.
- the process of the invention is capable of achieving TiO 2 (synthetic rutile) with a purity of 95wt% or more.
- the titanium oxide product may contain Fe 2 O 3 of 7.5wt% or less, preferably 6.5wt% or less, more preferably 2wt% or less.
- the titanium oxide product may contain Al 2 O 3 of 2.0wt% or less, preferably 1.5wt% or less, more preferably 0.9wt% or less.
- the titanium oxide product may contain SiO 2 of 1.5wt% or less, preferably lwt% or less, more preferably 0.75wt% or less, especially preferably 0.1 wt% or less.
- the titanium oxide product may contain U of 250ppm or less, preferably 200ppm or less, more preferably 155ppm or less, especially preferably 50ppm or less.
- the titanium oxide product may contain Th of 750ppm or less, preferably 600ppm or less, more preferably 580ppm or less.
- the titanium oxide product may contain Zr of 5500p ⁇ m or less, preferably 2500ppm or less, more preferably lOOOppm or less.
- Figure 1 illustrates a flow chart for beneficiation of a TiO 2 ore in accordance with an embodiment of the process of the invention
- Figure 2 is a photomicrograph of anatase ore after being subjected to an embodiment of the process of the invention
- Figure 3 is the microstructure of rutile grain in ilmenite ore after being subjected to an embodiment of the process of the invention.
- Ilmenite ore 1 (analysis given in Table 1) was homogeneously mixed with alkali carbonate (sodium or potassium) 2, alumina (20wt% of the ore) and CaO (3wt% of the ore) 3 to produce a charge 4.
- alkali carbonate sodium or potassium
- alumina (20wt% of the ore)
- CaO 3wt% of the ore
- a fine precipitate 6 of ore particles and hydroxides of ter alia Fe, Al, Nb, U, Th and REE was formed during washing and leaching and was separated out by filtration.
- the pH of the solution may be controlled by adding ammonium salts A for the separation and coarsening of the fine precipitate.
- the fine precipitate 6 was used for recovery Rl of metal values such as recovered additives 3 a and byproducts 20 (eg Fe 2 O 3 , Nb 2 O 5 ).
- Alkali salt, alumina, iron oxides/hydroxides and other metal values were recovered R2 from the leachate 8 of step C by CO 2 gas bubbling and/or organic acids B.
- step C The solid coarse residue 7 from step C was treated with 5% HCl acid solution 9 at 70°C for 10 minutes. The solution 9 was filtered and a solid residue 11 was thoroughly washed with dilute acid solution and then with water to remove all impurities.
- step F The leachate 10 from step F (containing acid soluble salts of inter alia Nb, U, Zr and REE) was treated for recovery R3 of acid and by-products 21 such as ZrO 2 , Nb 2 O 5 and Th/UO 2 .
- step F The solid residue 11 from step F was dried in an oven.
- the analysis of the product (synthetic rutile) is given in Table 1. It may be used for chlorination and the waste 22 from the chlorination plant may be subjected to recovery step R3.
- a part of the solid residue 11 from step H was roasted with NaHSO 4 (1 :1 ratio) at 300°C for 1 hour in air.
- the ratio of residue 11 : NaHSO 4 may be increased by carrying out its analysis for the remainder of impurities.
- step I The roasted mass from step I was leached with hot water at 80°C for 30 minutes. The solution was filtered and a further solid residue 12 was leached and washed repeatedly until the pH of the leach solution fell to 7.
- step J The further solid residue 12 from step J was dried in an oven.
- concentration of Fe O 3 , Al 2 O 3 , and SiO 2 in the final product had been reduced considerably to ⁇ 2 wt%, ⁇ 0.5 wt% and O.lwt % respectively.
- the purity of synthetic rutile after step J was therefore better than 95%.
- the purity of TiO 2 rises from 87% in unoptimized step H to 95% or more after step J.
- Table 1 Chemical composition of ilmenite ore and final product (synthetic rutile) after step H of the roasting-leaching process of Example I
- Figure 3 is the microstructure of rutile grain in ilmenite ore after alkali roasting and water leaching.
- the addition of 5 % (with respect to ore) CaO in the roasting charge accelerates the separation from rutile grain (grey colour) of solute impurities as a perovskite phase (bright phase).
- Anatase ore was subjected to steps identical to those described in Example I. In this case, no extra CaO was added in the roasting charge as ⁇ 2wt% CaO was present in the ore.
- the chemical analysis of the anatase ore and final product after the roasting and leaching steps is listed in Table 2.
- Figure 2 is a photomicrograph of anatase ore after alkali roasting at 850°C for 4 hours.
- the X-ray elemental map of grain A shows the formation of a Na-Al-Fe-Si-O complex phase
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Abstract
The present invention seeks to improve beneficiation of a titanium oxide-containing composition (such as a low-grade or highly radioactive TiO2 ore) by combining a roasting and selective leaching steps.
Description
PROCESS FOR THE RECOVERY OF TITANIUM DIOXIDE FROM TITANIUM-CONTAINING COMPOSITIONS
The present invention relates to a process for recovering titanium dioxide from a titanium oxide-containing composition such as an ore. Existing supplies of ilmenite and natural rutile are coming under pressure due to a steady growth in TiO2 markets and a rise in demand for high-grade ores for direct chlorination or for the production of synthetic rutile. The new beach sand/placer deposits are of variable quality and many are unsuitable for upgrading and beneficiation using existing commercial processes (Nameny 'Challenges and Opportunities in the TiO∑ Feedstock Industry ', AJM Global Mineral Sands Exploration and Investment Conference, Melbourne, 2003). Most TiO2-ores have high concentrations of zircon and monazite minerals due to their geological proximity. The zircon and monazite impurities in the feedstock reduce its market value. Actinide and lanthanide impurities create operational problems (eg high chlorine consumption or sticky beds) and generate hazardous waste with high concentrations of actinides, lanthanides and other heavy metals. Due to stringent environmental regulations in many countries, the treatment and disposal of such hazardous waste from pigment industries has become a major problem which is increasing the cost of waste treatment and management. Conventional processes for beneficiation of TiO ores are a) physical processes such as gravitational, magnetic and electrical separation which are used to separate the magnetite, monazite, zircon and other siliceous gangue and b) chemical processes, namely acid leaching and TiO2-slag formation (high temperature reduction) which are mainly used to remove iron (Becher, Benilite, Austpac).
However, these processes require high quality ilmenite ores. If used for beneficiation of low grade/highly radioactive TiO2-ores, the level of critical impurities such as Cr2O3, N2O5, Νb2O5 (which degrade the pigment properties) and CaO and SiO2 (which create operational problems such as sticky beds) is very high in the end product. Also solute
impurities (Fe, Nb, U, Th, Ce) in the TiO2 phases (pseudorutile, ilmenite, anatase) remain in the feedstock and end up in the waste stream of the pigment manufacturing process (chlorination or sulphatation). The slagging process (which is the main source of feedstock for pigment manufacturing) separates only iron oxides and most of the other impurities enter the feedstock eg in the TiO2-slags. The slagging process is also facing uncertainty due to its high power consumption and emission of greenhouse gas. In view of the changing sources (deposits) of TiO2 ores and environmental concerns in relation to the disposal of waste, there is a need for a more environmentally acceptable approach to the beneficiation of TiO2. There have been a number of investigations into the roasting of ilmenite with soda, mainly in a reducing atmosphere with carbon (ed Fathi Habashi, Handbook of Extractive Metallurgy, Vol. II, PubL: Wiley-NCH, Berlin, 1997). However the yield of TiO2 in this technique is not very high (<90wt%). The major drawback of this process is that neither is iron separated in the metallic form nor is a leachable product produced (Handbook of Extractive Metallurgy [supra]). A limited number of investigations have been carried out on oxidative alkali roasting techniques. However the yield of TiO2 and separation out of actinides and lanthanides is below the required levels for chlorination (US-A-6346223). The present invention seeks to improve beneficiation of a titanium oxide-containing composition (such as a low-grade or highly radioactive TiO2 ore) by combining roasting and selective leaching steps. In particular, the present invention relates to a beneficiation process for separation of non-lanthanide (eg Fe, Ca, Si, V and Cr), pre-lanthanide (eg Zr and Νb), lanthanide (eg Ce and Νd) and actinide (eg U and Th) impurities from titaniferrous deposits. Viewed from a first aspect the present invention provides a process for recovering a titanium dioxide product from a titanium oxide-containing composition comprising:
(a) providing the titanium oxide-containing composition with one or more alkali salts and with at least one of an alumina-containing material and a calcium oxide-containing material to produce a charge;
(b) oxidatively roasting the charge to produce a roasted mass; and
(c) recovering the titanium oxide product from the roasted mass.
The process of the invention may successfully upgrade a wide range of titanium oxide-containing compositions and produce a high purity titanium oxide product (preferably synthetic rutile) for direct use in pigment production (chlorination and sulphatation). By roasting in the presence of an alumina-containing material or a calcium oxide-containing material, the process of the invention may achieve a complete, efficient and economical separation out of large concentrations of iron oxides and lanthanide and actinide impurities which otherwise contribute to the feedstock in pigment production. The addition of an alumina-containing material or a calcium oxide-containing material helps to remove not only zircon and monazite minerals but also lanthanide and actinide impurities (solute) present in the lattice of the TiO2 phases (rutile, pseudorutile, brookite, etc). In certain embodiments, the process also recovers metal values as value-added byproducts and alkali salts thereby substantially reducing the amount of waste and usage of raw materials (namely alkali salt and alumina) which can be recycled to make the process economically viable. By "titanium oxide-containing compositio '' is meant a mixture of metal oxide species in compound form or forms which include titania (TiO2). The titanium oxide- containing composition may be synthetic or (preferably) natural such as a powder, ore or mineral or a mixture thereof. Preferred is a titanium rich material such as an ore (eg ilmenite, anatase, ilmenite beach sands, low grade titaniferrous slag, natural rutile or perovskite). Preferred are titaniferrous mixtures which further include at least one iron species such as a ferrous or ferric species (preferably an iron oxide such as FeO, Fe2O3 or Fe3O4). The titaniferrous mixture may further comprise alumina or silica. The titanium oxide-containing composition may be a residue from a chlorination or sulphatation process. Preferably the mineral ores are selected from the group consisting of ilmenite, anatase and perovskite. Preferably the mineral ore is a mixture of ilmenite and perovskite. Preferably the one or more alkali salts is one or more alkali metal or alkaline earth metal salts. Preferably the one or more alkali salts is one or more carbonates, hydroxides, bicarbonates or sulphates of a group IA or group IIA metal or a mixture thereof. For
example, the one or more alkali salts may be selected from the group consisting of Na2CO3, K2CO3, Na2SO4, K2SO4, NaOH, NaHSO4, KHSO4, KHCO3, NaHCO3 and KOH. Sodium and/or potassium carbonate are preferred. The amount of alkali salt may be calculated based on the formation of alkali compounds of TiO2, Fe2O3, Al2O3, SiO2, and P2O5 present in the composition (eg ore). Preferably step (a) comprises: providing the titanium oxide-containing composition with one or more alkali salts and with an alumina-containing material and a calcium oxide-containing material. Step (b) may be carried out at a temperature in the range 500°C to 1000°C, preferably 700°C to 975°C, more preferably 700°C to 875°C (eg about 800°C) in air or another source of oxygen. Step (b) may be carried out in a conventional rotary kiln or a rotary hearth furnace. Step (b) may be carried out for a suitable length of time (eg 120 minutes). Step (b) generally forms alkali titanates and complex oxide salts. Step (a) typically includes mixing (eg homogeneously mixing) the titanium oxide- containing composition with one or more alkali salts and with at least one of the alumina- containing material and the calcium oxide-containing material to produce the charge. The alumina-containing material or calcium oxide-containing material may undergo controlled addition to the titanium oxide-containing composition. Preferably the alumina-containing material (eg alumina) is present in the charge in an amount in the range 5 to 30wt% of the titanium oxide-containing composition, preferably 10 to 25wt% of the titanium oxide-containing composition, more preferably 15 to 22wt% (eg about 20wt%) of the titanium oxide-containing composition. The precise amount of alumina-containing materials in the charge generally depends on the ratio of titanium oxide-containing compositio alkali salt, formation of liquid phase and the concentration of various impurities (mainly iron oxides, silicates and phosphates). The alumina-containing material may be alumina, aluminum hydroxide, Al2O -containing clay or a mixture thereof. An aluminate (egNaAlO2) may also be used. During step (b), alumina along with other gangue phases in the titanium oxide-containing composition react with the alkali salt and form complex oxide phases (such as Na-Al-Si-M-O phases)
which increase the solubility and stability of ferrites such as sodium ferrite. This complex salt phase thereby helps to separate out iron oxides from the titanium oxide-containing composition. The calcium oxide-containing material may be lime (ie CaO or Ca(OH)2), calcium oxide (eg calcite) or a mixture thereof. Preferably the calcium oxide-containing material (eg CaO) is present in the charge in an amount in the range 0.1 to 5wt% of the titanium oxide-containing composition, preferably 1 to 4wt% of the titanium oxide-containing composition, more preferably 2 to 3wt% of the titanium oxide-containing composition. The addition of the calcium oxide-containing material is on the basis of the formation of perovskite and pyrochlore-type phases of TiO2 and ZrO2 which can dissolve high concentrations of inter alia rare earth elements REEs (eg U or Th) and Nb (De Hoog et al, Mineralogical Magazine, 61, 721-725, 1997). During step (b), CaO reacts with TiO2 and zircon minerals and forms various Ca-Na-Ti-M-O compounds such as perovskite (CaTiO3), zirconolite [(Ca,Fe,Y,Th)2(Fe,Ti,Nb)3Zr2O7] and hiarneite [(Ca,Mn,Na)2(Zr,Mn)5(Sb,Ti,Fe)2O16] which advantageously absorb most of the lanthanide and actinide impurities in the monazite and zircon minerals. The solute impurities in the TiO2-rich phases diffuse outward towards the CaTiO3 formed on the surface of TiO2 grains. Step (c) may comprise: (cl) adding to the roasted mass an aqueous medium to produce an aqueous solution and a substantially insoluble residue.
The aqueous medium may be water or an alkali solution (eg a dilute alkali solution). Typically water is used at an elevated temperature. The hot water may be at a temperature in the range 70 to 90°C. Step (cl) may be carried out in hot water for 20 to 200 minutes, preferably 25 to 100 minutes (eg 40 minutes). In step (cl), water-soluble alkali compounds such as metal (eg sodium) aluminate, silicate, chromate, vanadate and phosphate may be dissolved in the aqueous solution. Aqueous medium may be added repeatedly to wash the substantially insoluble residue (typically until the pH of the washings reaches about 7). Preferably step (cl) comprises:
(cla) adding water at an elevated temperature to the roasted mass to produce an aqueous solution and a substantially insoluble residue;
(clb) adding to the aqueous solution a source of alkalinity to enhance the selective separation of a fine precipitate.
The fine precipitate generally comprises fine particles of titanium oxide-containing composition (eg ore) and constituents of complex alkali salts (eg Na-Al-Si-Fe-M-O) which precipitate as oxides or hydroxides of Fe, Nb, Al or RREs (eg U and Th) due to their limited solubility. The fine precipitate may be separated from the aqueous solution by standard techniques such as filtration. The source of alkalinity is preferably an ammonium salt such as a carbonate, sulphate, bisulphate or bicarbonate. Typically the ammonium salt is added in an amount up to 5wt% to optimize precipitation kinetics. Preferably the process further comprises: (d) recovering metal values from the fine precipitate.
In step (d), the metal values may be selected from the group consisting of alumina- containing material (eg alumina), calcium oxide-containing material (eg CaO) and metal oxides (eg iron oxide such as Fe2O3 or niobium oxide such as Nb2O5). Preferably the process further comprises: (e) recovering metal values from the aqueous solution. In step (e), the metal values may be selected from the group consisting of alkali salt, alumina-containing material (eg alumina), calcium oxide-containing material (eg CaO) V2O5, Fe2O3 and Cr2O3. Oxides of Nb, Ta, Zr and RREs may also be recovered (eg NbO, ZrO2, U3O8, UO2, UO3, ThOx). Preferably step (e) comprises: (el) acidifying the aqueous solution. Step (el) may be performed by the addition of a weak acid. Typically the acid is an inorganic acid (eg an inorganic acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, nitric acid, sulphuric acid, an acidic oxide and mixtures thereof). Step (el) may be better controlled by using a weak organic acid such as formic, oxalic or acetic acid and/or CO2. Preferably the acid is an acidic oxide, particularly preferably
carbon dioxide. For example, step (el) may include: bubbling CO2 gas through (or passing oxalic acid into) the aqueous solution. The addition of weak acid and/or CO2 provides precise control of pH for selective precipitation of oxides. The use of an acid with CO2 also helps precipitation coarsening kinetics and therefore reduces the entrapment of small particles of impurity oxides with coarser TiO2-rich particles in the coarse residue. By recovering metal values as value-added byproducts and alkali salts in steps (d) and (e), the amount of waste and usage of raw material (namely alkali carbonate and alumina) is reduced to make the process economically viable. Step (c) of the process preferably further comprises: (c2) acid leaching the substantially insoluble residue to produce an acid leachate and a solid residue consisting essentially of titanium oxide. Step (c2) may be carried out in an acid solution, preferably an inorganic acid solution (such as a 2-10% mineral acid (eg HC1, HNO3 or H2SO4) solution). An example of a suitable acid is 5% HC1. Preferably the acid is at an elevated temperature (eg 70- 90°C). Step (c2) may be carried out for 5 to 200 minutes, preferably 5 to 100 minutes (eg 10 minutes). The concentration of acid and solid-to-liquid ratio are generally based on the amount of insoluble salts of Fe2O3, SiO2 and CaO compounds in the substantially insoluble residue from step (cl). The solid residue may be separated from the acid leachate by standard techniques such as filtration. In step (c2), acid-soluble salts of inter alia Nb, Zr and REEs (eg U and Th) may be dissolved in the acid leachate. Alkali titanates are decomposed to TiO2. Dilute acid (and optionally then water) may be added repeatedly to wash the solid residue. Preferably step (c2) comprises: (c2a) recovering metal values from the acid leachate. In step (c2a), the metal values may be selected from the group consisting of acidic compounds, alkali compounds and oxides. Specific examples are ZrO2, Nb2Os and Th/UO2. Typically the solid residue after step (c2) is TiO2-rich and may comprise 87wt% or more of TiO2 (dependent upon the fineness of oxides produced in step (el)), preferably
87-95wt%. Further purification of the solid residue may be carried out (eg by electrolytic purification techniques or calcining). Calcining may be carried out using alkali bisulphates and bicarbonates to further reduce levels of iron, aluminium, silica, phosphate, lanthanide and actinide to produce whiter grades of synthetic rutile. Purification and agglomeration of the solid residue may form synthetic rutile with a desired level of purity and particle size distribution. Preferably step (c) of the process further comprises: (c3) roasting at least a proportion of the solid residue with one or more alkali hydrogen sulphates and/or carbonates to produce a roast.
Preferably step (c3) is carried out at low temperature such as 200-400°C (eg at about 300°C) in air or another source of oxygen for 1 to 4 hours. Preferred alkali hydrogen sulphates are NaHSO4 and/or KHSO4. Typically the ratio of NaHSO4 or KHSO4 to solid residue is about 1 :1. Typically step (c3) is carried out for 1 hour. Step (c) of the process preferably further comprises: (c4) water leaching the roast to produce the titanium oxide product. Typically water is used in step (c4) at an elevated temperature. The hot water may be at a temperature in the range 70 to 90°C. Step (c4) may be carried out in hot water for 20 to 200 minutes, preferably 25 to 100 minutes (eg 30 minutes). The titanium oxide product may be separated from the water leachate by standard techniques such as filtration. Water and optionally dilute acid solution may be added repeatedly to wash the roast (typically until the pH of the washings reaches about 7). The titanium oxide product is preferably in the form of synthetic rutile. The process of the invention is capable of achieving TiO2 (synthetic rutile) with a purity of 95wt% or more. The titanium oxide product may contain Fe2O3 of 7.5wt% or less, preferably 6.5wt% or less, more preferably 2wt% or less. The titanium oxide product may contain Al2O3 of 2.0wt% or less, preferably 1.5wt% or less, more preferably 0.9wt% or less. The titanium oxide product may contain SiO2 of 1.5wt% or less, preferably lwt% or less, more preferably 0.75wt% or less, especially preferably 0.1 wt% or less.
The titanium oxide product may contain U of 250ppm or less, preferably 200ppm or less, more preferably 155ppm or less, especially preferably 50ppm or less. The titanium oxide product may contain Th of 750ppm or less, preferably 600ppm or less, more preferably 580ppm or less. The titanium oxide product may contain Zr of 5500pρm or less, preferably 2500ppm or less, more preferably lOOOppm or less. The present invention will now be described in a non-limitative sense with reference to the accompanying Examples and Figures in which: Figure 1 illustrates a flow chart for beneficiation of a TiO2 ore in accordance with an embodiment of the process of the invention; Figure 2 is a photomicrograph of anatase ore after being subjected to an embodiment of the process of the invention; and Figure 3 is the microstructure of rutile grain in ilmenite ore after being subjected to an embodiment of the process of the invention.
EXAMPLE I: Ilmenite Ore from Australia
In one embodiment of the invention illustrated in Figure 1, the following steps are involved in the beneficiation of ilmenite ore. A. Ilmenite ore 1 (analysis given in Table 1) was homogeneously mixed with alkali carbonate (sodium or potassium) 2, alumina (20wt% of the ore) and CaO (3wt% of the ore) 3 to produce a charge 4. B. The charge 4 was roasted in air at 950°C for 120 minutes to produce a roasted mass. C. The roasted mass was leached with hot water 5 at 80°C for 40 minutes. The solution was filtered and a solid coarse residue 7 was leached and washed repeatedly until the pH of the leachate 8 fell to seven. D. A fine precipitate 6 of ore particles and hydroxides of ter alia Fe, Al, Nb, U, Th and REE was formed during washing and leaching and was separated out by
filtration. The pH of the solution may be controlled by adding ammonium salts A for the separation and coarsening of the fine precipitate. The fine precipitate 6 was used for recovery Rl of metal values such as recovered additives 3 a and byproducts 20 (eg Fe2O3, Nb2O5).
E. Alkali salt, alumina, iron oxides/hydroxides and other metal values were recovered R2 from the leachate 8 of step C by CO2 gas bubbling and/or organic acids B.
F. The solid coarse residue 7 from step C was treated with 5% HCl acid solution 9 at 70°C for 10 minutes. The solution 9 was filtered and a solid residue 11 was thoroughly washed with dilute acid solution and then with water to remove all impurities.
G. The leachate 10 from step F (containing acid soluble salts of inter alia Nb, U, Zr and REE) was treated for recovery R3 of acid and by-products 21 such as ZrO2, Nb2O5 and Th/UO2.
H. The solid residue 11 from step F was dried in an oven. The analysis of the product (synthetic rutile) is given in Table 1. It may be used for chlorination and the waste 22 from the chlorination plant may be subjected to recovery step R3.
I. A part of the solid residue 11 from step H was roasted with NaHSO4 (1 :1 ratio) at 300°C for 1 hour in air. The ratio of residue 11 : NaHSO4 may be increased by carrying out its analysis for the remainder of impurities.
J. The roasted mass from step I was leached with hot water at 80°C for 30 minutes. The solution was filtered and a further solid residue 12 was leached and washed repeatedly until the pH of the leach solution fell to 7.
K. The further solid residue 12 from step J was dried in an oven. The concentration of Fe O3, Al2O3, and SiO2 in the final product had been reduced considerably to <2 wt%, <0.5 wt% and O.lwt % respectively. The purity of synthetic rutile after step J was therefore better than 95%.
In summary, the purity of TiO2 rises from 87% in unoptimized step H to 95% or more after step J.
Table 1: Chemical composition of ilmenite ore and final product (synthetic rutile) after step H of the roasting-leaching process of Example I
Figure 3 is the microstructure of rutile grain in ilmenite ore after alkali roasting and water leaching. The addition of 5 % (with respect to ore) CaO in the roasting charge accelerates the separation from rutile grain (grey colour) of solute impurities as a perovskite phase (bright phase).
EXAMPLE II: Anatase ore
Anatase ore was subjected to steps identical to those described in Example I. In this case, no extra CaO was added in the roasting charge as ~2wt% CaO was present in the ore. The
chemical analysis of the anatase ore and final product after the roasting and leaching steps is listed in Table 2.
Table 2: Chemical composition of anatase ore and final product (synthetic rutile) after the roasting-leaching process of Example II
Figure 2 is a photomicrograph of anatase ore after alkali roasting at 850°C for 4 hours. The X-ray elemental map of grain A shows the formation of a Na-Al-Fe-Si-O complex phase
Claims
1. A process for recovering a titanium dioxide product from a titanium oxide- containing composition comprising:
(a) providing the titanium oxide-containing composition with one or more alkali salts and with at least one of an alumina-containing material and a calcium oxide-containing material to produce a charge;
(b) oxidatively roasting the charge to produce a roasted mass; and
(c) recovering the titanium oxide product from the roasted mass.
2. A process as claimed in claim 1 wherein the titanium oxide-containing composition is an ore.
3. A process as claimed in claim 1 or 2 wherein the titanium oxide-containing composition is a titaniferrous mixture.
4. A process as claimed in claim 2 wherein the ore is selected from the group consisting of ilmenite, anatase and perovskite.
5. A process as claimed in any preceding claim wherein the one or more alkali salts is one or more carbonates, hydroxides, bicarbonates or sulphates of a group la or group Ila metal or a mixture thereof.
6. A process as claimed in claim 5 wherein the one or more alkali salts is selected from the group consisting of Na2CO3, K2CO3, Na2SO4, K2SO , NaOH, NaHSO4, KHSO , KHCO3, NaHCO3 and KOH.
7. A process as claimed in claim 5 or 6 wherein the one or more alkali salts is selected from the group consisting of sodium and potassium carbonate.
8. A process as claimed in any preceding claim wherein step (a) comprises: providing the titanium oxide-containing composition with one or more alkali salts and with an alumina-containing material and a calcium oxide-containing material.
9. A process as claimed in any preceding claim wherein the alumina-containing material is selected from the group consisting of alumina, aluminum hydroxide, AI2O3- containing clay, NaAlO2 and mixtures thereof.
10. A process as claimed in any preceding claim wherein the calcium oxide- containing material is selected from the group consisting of lime, calcium oxide and mixtures thereof.
11. A process as claimed in any preceding claim wherein step (c) comprises:
(cl) adding to the roasted mass an aqueous medium to produce an aqueous solution and a substantially insoluble residue.
12. A process as claimed in claim 11 wherein the aqueous medium is water or an alkali solution.
13. A process as claimed in claim 11 or 12 wherein the aqueous medium is hot water.
14. A process as claimed in claim 11, 12 or 13 wherein step (cl) comprises:
(cla) adding water at an elevated temperature to the roasted mass to produce an aqueous solution and a substantially insoluble residue;
(clb) adding to the aqueous solution a source of alkalinity to enhance the selective separation of a fine precipitate.
15. A process as claimed in claim 14 wherein the source of alkalinity is an ammonium salt.
16. A process as claimed in claim 14 or 15 further comprising: (d) recovering metal values from the fine precipitate.
17. A process as claimed in claim 16 wherein the metal values are selected from the group consisting of alumina-containing material, calcium oxide-containing material and metal oxides.
18. A process as claimed in any of claims 11 to 17 further comprising: (e) recovering metal values from the aqueous solution.
19. A process as claimed in claim 18 wherein the metal values are selected from the group consisting of alkali salt, alumina-containing material, calcium oxide-containing material, V2O5, Fe2O3 and Cr2O3.
20. A process as claimed in claim 18 or 19 wherein step (e) comprises: (el) acidifying the aqueous solution.
21. A process as claimed in claim 20 wherein step (el) is performed by the addition of a weak organic acid.
22. A process as claimed in claim 21 wherein the weak organic acid is formic, oxalic or acetic acid and/or CO2.
23. A process as claimed in any of claims 11 to 22 wherein step (c) further comprises: (c2) acid leaching the substantially insoluble residue to produce an acid leachate and a solid residue consisting essentially of titanium oxide.
24. A process as claimed in claim 16 wherein step (c2) comprises: (c2a) recovering metal values from the acid leachate.
25. A process as claimed in either of claims 23 and 24 wherein step (c) of the process further comprises: (c3) roasting at least a proportion of the solid residue with one or more alkali hydrogen sulphates and/or carbonates to produce a roast.
26. A process as claimed in claim 25 wherein the alkali hydrogen sulphates are NaHSO4 or KHSO4.
27. A process as claimed in claim 25 or 26 wherein step (c) of the process comprises: (c4) water leaching the roast to produce the titanium oxide product.
28. A process as claimed in claim 27 wherein water is used in step (c4) at an elevated temperature.
29. A process as claimed in any preceding claim wherein the titanium oxide product has a purity of 95wt% or more.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES04768471T ES2709399T3 (en) | 2003-09-18 | 2004-09-14 | Recovery procedure for titanium dioxide from titanium-containing compositions |
| US10/571,038 US7771679B2 (en) | 2003-09-18 | 2004-09-14 | Process for the recovery of titanium dioxide from titanium-containing compositions |
| BRPI0414516A BRPI0414516B1 (en) | 2003-09-18 | 2004-09-14 | process for recovering titanium dioxide from compositions containing titanium |
| EP04768471.7A EP1663871B1 (en) | 2003-09-18 | 2004-09-14 | Process for the recovery of titanium dioxide from titanium-containing compositions |
| JP2006526683A JP5142524B2 (en) | 2003-09-18 | 2004-09-14 | Method for recovering titanium dioxide from a titanium-containing composition |
| CA2539537A CA2539537C (en) | 2003-09-18 | 2004-09-14 | Process for the recovery of titanium dioxide from titanium-containing compositions |
| AU2004274226A AU2004274226B2 (en) | 2003-09-18 | 2004-09-14 | Process for the recovery of titanium dioxide from titanium-containing compositions |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0321845.0A GB0321845D0 (en) | 2003-09-18 | 2003-09-18 | Removal of actinide & lanthanide impurities from the titani-ferrous deposits and wastes |
| GB03218450.0 | 2003-09-18 | ||
| GBPCT/GB04/002543 | 2004-06-11 | ||
| PCT/GB2004/002543 WO2004113230A1 (en) | 2003-06-16 | 2004-06-11 | Extraction process for reactive metal oxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2005028369A1 true WO2005028369A1 (en) | 2005-03-31 |
| WO2005028369B1 WO2005028369B1 (en) | 2005-05-19 |
Family
ID=34379483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2004/003925 WO2005028369A1 (en) | 2003-09-18 | 2004-09-14 | Process for the recovery of titanium dioxide from titanium-containing compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1663871B1 (en) |
| JP (1) | JP5142524B2 (en) |
| AU (1) | AU2004274226B2 (en) |
| CA (1) | CA2539537C (en) |
| WO (1) | WO2005028369A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007091342A1 (en) * | 2006-02-08 | 2007-08-16 | Niigata University | Method of synthesizing titanium oxide via nitric acid solution |
| WO2010032052A1 (en) * | 2008-09-17 | 2010-03-25 | Millennium Inorganic Chemicals Limited | Process for recovering a titanium dioxide product |
| WO2012051424A2 (en) * | 2010-10-15 | 2012-04-19 | Cic Resources Inc. | Method for processing ilmenite-containing mineral materials with high clay content, and related products |
| WO2016139460A1 (en) * | 2015-03-04 | 2016-09-09 | University Of Leeds | Process |
| WO2016139461A1 (en) * | 2015-03-04 | 2016-09-09 | University Of Leeds | Process |
| CN113416847A (en) * | 2021-07-05 | 2021-09-21 | 昆明理工大学 | Method for recycling, reducing and harmlessly treating vanadium extraction tailings |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1911396A (en) * | 1932-11-29 | 1933-05-30 | Southern Mineral Products Corp | Process of treating titaniferous ores |
| WO2002010068A1 (en) * | 2000-07-29 | 2002-02-07 | University Of Leeds | Production of metal oxides |
| US6346223B2 (en) * | 1997-10-17 | 2002-02-12 | Companhia Vale Do Rio Doce | Process for the production of titanium concentrate from anatase ores with high utilization of the iron contents of the ore |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3733193A (en) * | 1970-07-22 | 1973-05-15 | Union Carbide Corp | Recovery of vanadium from titaniferous iron ores |
| JPH02111627A (en) * | 1988-10-19 | 1990-04-24 | Mitsubishi Heavy Ind Ltd | Treatment of red mud |
| US5181956A (en) * | 1990-03-08 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Method for purifying TiO2 ore |
| GB9600196D0 (en) * | 1996-01-05 | 1996-03-06 | Tioxide Group Services Ltd | Preparation of anatase titanium dioxide |
| JPH11349329A (en) * | 1998-04-07 | 1999-12-21 | Mitsubishi Materials Corp | Titanium dioxide having excellent color stability and its production |
-
2004
- 2004-09-14 WO PCT/GB2004/003925 patent/WO2005028369A1/en active Application Filing
- 2004-09-14 JP JP2006526683A patent/JP5142524B2/en not_active Expired - Fee Related
- 2004-09-14 AU AU2004274226A patent/AU2004274226B2/en not_active Ceased
- 2004-09-14 CA CA2539537A patent/CA2539537C/en not_active Expired - Fee Related
- 2004-09-14 EP EP04768471.7A patent/EP1663871B1/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1911396A (en) * | 1932-11-29 | 1933-05-30 | Southern Mineral Products Corp | Process of treating titaniferous ores |
| US6346223B2 (en) * | 1997-10-17 | 2002-02-12 | Companhia Vale Do Rio Doce | Process for the production of titanium concentrate from anatase ores with high utilization of the iron contents of the ore |
| WO2002010068A1 (en) * | 2000-07-29 | 2002-02-07 | University Of Leeds | Production of metal oxides |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007091342A1 (en) * | 2006-02-08 | 2007-08-16 | Niigata University | Method of synthesizing titanium oxide via nitric acid solution |
| WO2010032052A1 (en) * | 2008-09-17 | 2010-03-25 | Millennium Inorganic Chemicals Limited | Process for recovering a titanium dioxide product |
| US7964164B2 (en) | 2008-09-17 | 2011-06-21 | Millennium Inorganic Chemicals, Inc. | Process for recovering titanium dioxide |
| WO2012051424A2 (en) * | 2010-10-15 | 2012-04-19 | Cic Resources Inc. | Method for processing ilmenite-containing mineral materials with high clay content, and related products |
| WO2012051424A3 (en) * | 2010-10-15 | 2012-07-19 | Cic Resources Inc. | Method for processing ilmenite-containing mineral materials with high clay content, and related products |
| WO2016139460A1 (en) * | 2015-03-04 | 2016-09-09 | University Of Leeds | Process |
| WO2016139461A1 (en) * | 2015-03-04 | 2016-09-09 | University Of Leeds | Process |
| US10508320B2 (en) | 2015-03-04 | 2019-12-17 | University Of Leeds | Process for recovering primary metal residue from a metal-containing composition |
| AU2016227471B2 (en) * | 2015-03-04 | 2021-07-15 | University Of Leeds | Process |
| CN113416847A (en) * | 2021-07-05 | 2021-09-21 | 昆明理工大学 | Method for recycling, reducing and harmlessly treating vanadium extraction tailings |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5142524B2 (en) | 2013-02-13 |
| AU2004274226A1 (en) | 2005-03-31 |
| CA2539537C (en) | 2012-11-27 |
| EP1663871A1 (en) | 2006-06-07 |
| CA2539537A1 (en) | 2005-03-31 |
| AU2004274226B2 (en) | 2010-03-04 |
| JP2007505812A (en) | 2007-03-15 |
| WO2005028369B1 (en) | 2005-05-19 |
| EP1663871B1 (en) | 2018-11-07 |
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