CA1079488A - Treatment method of raw materials containing titanium - Google Patents
Treatment method of raw materials containing titaniumInfo
- Publication number
- CA1079488A CA1079488A CA251,611A CA251611A CA1079488A CA 1079488 A CA1079488 A CA 1079488A CA 251611 A CA251611 A CA 251611A CA 1079488 A CA1079488 A CA 1079488A
- Authority
- CA
- Canada
- Prior art keywords
- ions
- aqueous solution
- organic extractant
- titanium
- hcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002994 raw material Substances 0.000 title claims abstract description 19
- 239000010936 titanium Substances 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 39
- 229910052719 titanium Inorganic materials 0.000 title claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000011084 recovery Methods 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims description 98
- 239000007864 aqueous solution Substances 0.000 claims description 64
- 239000003960 organic solvent Substances 0.000 claims description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 55
- -1 Fe3+ ions Chemical class 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 30
- 229910001447 ferric ion Inorganic materials 0.000 claims description 28
- 150000001412 amines Chemical group 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 15
- 239000010955 niobium Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 235000011007 phosphoric acid Nutrition 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003141 primary amines Chemical class 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910011011 Ti(OH)4 Inorganic materials 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 2
- 239000011572 manganese Substances 0.000 claims 2
- 239000003209 petroleum derivative Substances 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 235000012501 ammonium carbonate Nutrition 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 26
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000004090 dissolution Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 7
- 150000001455 metallic ions Chemical class 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 6
- 229910004356 Ti Raw Inorganic materials 0.000 abstract description 5
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 63
- 239000012074 organic phase Substances 0.000 description 20
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 229910015400 FeC13 Inorganic materials 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 229960004838 phosphoric acid Drugs 0.000 description 6
- 238000005201 scrubbing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical compound CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102220625805 Eosinophil peroxidase_I40M_mutation Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- GUBGYTABKSRVRQ-QRZGKKJRSA-N beta-cellobiose Chemical compound OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QRZGKKJRSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 description 1
- QZIQJVCYUQZDIR-UHFFFAOYSA-N mechlorethamine hydrochloride Chemical compound Cl.ClCCN(C)CCCl QZIQJVCYUQZDIR-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WVPGXJOLGGFBCR-UHFFFAOYSA-N trioctyl phosphate Chemical compound CCCCCCCCOP(=O)(OCCCCCCCC)OCCCCCCCC WVPGXJOLGGFBCR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0488—Flow sheets
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- 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
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
Production of titanium dioxide which is characterized by recovery of reusable H2SO4, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc. from FeSO4?nH2O and waste acid of 20 - 40% H2SO4 containing abundant heavy metallic ions which are by-produced in the production of TiO2 by dis-solution of Ti raw materials such as ilmenite, steel production slag, such as electric furnace slag, convertor slag with H2SO4.
Production of titanium dioxide which is characterized by recovery of reusable H2SO4, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc. from FeSO4?nH2O and waste acid of 20 - 40% H2SO4 containing abundant heavy metallic ions which are by-produced in the production of TiO2 by dis-solution of Ti raw materials such as ilmenite, steel production slag, such as electric furnace slag, convertor slag with H2SO4.
Description
~07948~
This invention is concerned with the production of titanium dioxide which i9 characterized by recovery of reusable H2S04, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc. from FeS04.nH20 and waste acid of 20 - 4~/0 H2S04 containing abundant heavy metallic ions, which are by-produced in the production of TiO2 by dissolution of Ti raw mate-rial~ such as ilmenite, steel production slag, quch as electric furnace slag, convertor slag with H2S04.
In the conventional production o~ TiO2 using H2S04, the required 98% H2S04 per 1 ton of TiO2 product is 3.5 to 4.2 tons.
Nevertheless, the economical treatment of FeS04.nH20 and waste acid~ by-produced in abundance after the separation of Ti com-pounds by hydrolysis process has not been found and the allow-ance to stand or discard them as untreatment has given rise to serious pollution problems. This invention is originated to over-come the faults of the conventional production process described above.
The present invention relates to a production of ti-tanium dioxide which is characterized by recovery of reusable H2S04, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc. from FeS04.nH20 and waste acid of 20 - 40YO
H2S04 containing abundant heavy metallic ions, which are by-pro-duced in the production of TiO2 by dissolutlon of Ti raw materials such as ilmenite, steel production slag, such as electric furnace slag, convertor slag w th H2S04.
The Qummary of this invention is as follows. The pre-sent invention iB firstly characterized with~ production of waste acids and FeS04.nH20 as follows. The aqueou~ solution pretreated after dissolution of Ti raw materials with H2S04 is brought into contact and mixed with an organic solvent (A) to extract metallic ions such as Cr3+ and Nb5+ ions in the first st~ge and the bulk of Ti ions in the resulting aqueous solution 10794~8 is separated by well-known hydrolysis process in the 2nd stage, The rnetallic ions such as Ti, Mn and V ions remaining in the re-sult:ing aqueous solution are extracted into an organic solvent (B) ln the 3rd stage, an organic solvent (C) extracts Fe ions in the resulting aqueous solution after the oxidation of Fe2+
ions to Fe ions in the 4th stage and V5+ ions in the resulting aqueous solution are extracted into an organic solvent (D) in the 5th stage, The resulting aqueous solution from the 5th stage is the reusable regenerated acid for dissolution of raw materials.
The 2nd characteristic OL present invention is con-cerned with the extraction of Fe ions from the aqueous solution using C12 gas for the oxidation as follows. After the conversion of Fe2+ ions in the aqueous solution from the 3rd stage to Fe3 ions using C12 gas, the amount of HCl required to extract Fe3 ions in the aqueous solution as Fe chloride complex is added to the resulting aqueous solution and is contacted with an organic solvent (E) to extract Fe-Cl ions into the organic phase, The 3rd characteristic of this invention is concerned with the reduction of energy in concentration process of acid as follows. FeS04.nH20 by-produced in the pretreatment process is dissolved with water or acids from the 4th stage, the oxidation of Fe + ions in the resulting aqueous solution to Fe ions is finished and then Fe3+ ions in the resulting aqueous solution are extracted into the organic phase with contact of the organic' solvent ~C). The increasing concentration of regenerated acid by several repetitions of the above operation in compliance with dema,nd yields the reduction of energy in the following concen-tration process of acid.
The 4th characteristic of present invention is con-cerned with the reasonable treatment of FeS04.nH20 with the fractional extraction of Mn and Fe ions as follows. After dis-solution of FeS04'nH20 by-produced with water, Mn + ions in the resulting aqueous solution are extracted with an organic solvent 10794~8 (F) into th~ organic phase to separate from ~e ions in the re-sulting aqueous solution, Fe2+ ions are oxidized to Fe3+ ions and then Fe3+ ions are extracted into the organic phase with contact of the organic solvent (C). The concentration of recovered acid is enhanced by several repetitions of the above operation in eom-pliance with demand and recycled for dissolution of raw materials by way of the eoncentration proeess The 5th charaeteristie of this invention is concerned with the reduetion of reeovery cost by rising Fe concentration in the aqueous solution introduced into the recovery process of HCl and Fe as follows. The Fe concentration of the aqueous solution introduced into the reeovery proeess of HCl and Fe is increased by extracting Fe3+ ions in the baek-extraction solution of the organie solvent (C) with eontaet of the organic solvent (E) and stripping with water. The inereased Fe eoneentration produees the reduetion of reeovery eost.
The 6th eharaeteristie of this invention is concerned with the reasonable recovery of Fe compounds using both solvent extraction and diaphragm-eleetrolysis teehniques as follows.
The baek-extraetion solution of the organie solvent (C) or of the organie-solvent (E) is introdueed into the eathode eompartment of diaphragm-eleetrolysis, Fe3+ ions are reduced to Fe ions there, free acid is transferred to the anode eompartment and hydrated Fe oxide or hydroxide is reeovered with eontaet of air or oxygen and the aqueous solution in the eathode eompartment eontaining a lesser amount of free reeovered aeid.
The 7th eharaeteristic of this invention is concerned with the fraetional reeovery of metallie ions eoextraeted into the organie solvent (B) as follows. Mn, V and Fe ions coextraeted`
into the organie solvent (B) are serubbed with HCl or H2S04, Ti ions in the organie solvent (B) is baek-extraeted into the aqueous solu-tion with eontaet of (NH4)2C03 + NH3 solution, and then the organie 1079~88 solvent converted from H type to N~I3 type in the above operationis ac~ain converted to H type with contact of H2S04. When Cr3 ions are coextracted, they in the organic phase can be recovered into the aqueous solution with contact of HCl ~ H202 or HCl +
NaCl solution. Thus, the individual metallic ion coextracted into the organic solvent (B) is fractionally recovered. When A13+ and Mg2 ions are accumulated in the recovered acid during recycle of recovered acid, the enhacement of their ions concen-tration is depressed by taking one part of them out of the extraction system and the solution taken out is recovered as (NH4)2S04 by neutralizing with NH3.
The invention relatec to a process for the prepara-tion of titanium dioxide by dissolving titanium-containing raw materials in ~ulphuric acid to form an aqueous solution of sulphuric acid containing dissolved titanium and other metals, separating ferrous sulphate from the aqueous solution and then isolating titanium as the desired titanium dioxide by the steps of:
a) where dissolved chromium and niobium are present in the aqueous solution, contacting the aqueous solution with an organic extractant ~A) capable of extracting chromium and niobium so as to extract the dissolved chromium and niobium from the a~ueous solution, b) hydrolysing the aqueous solution so as to precipitate the majority of dissolved titanium therefrom and subsequently recovering the precipitated titanium compound as titanium dioxide;
c) contacting the hydrolysed aqueous solution with an organic extractant (B) capable of extracting titanium from the aqueous solution for subsequent recovery as titanium dioxide:
~ -4-10~5~48~
d) oxidizing the thus-contacted aqueous solution to convert ferrous ions present therein -to ferric ions and contacting the oxidized aqueous solution with an organic extractant (c) capable of extracting ferric ions so as to extract ferric ions from the aqueous solution; and where dissolved vanadium is present in the aqueous solution;
e) contacting the resultant aqueous solution with an organic extractant (D) capable of extracting vanadium so as to extract dissolved vanadium from the aqueous solution to yield a liquor essentially comprising sulphuric acid substantially free from dissolved chromium, niobium, titanium, iron and vanadium.
- 4a -107948~
FIGURE 7 is a graph showing Ti ion extraction equi-librium curve in the third stage, FIGURE 8 is a graph showing Ti ion back-extraction equilibrium curve in the third stage' FIGURE 9 is a graph showing Cr3+ ion back-extraction equilibrium curve in the third stage, FIGURE 10 is a graph showing Fe3 ion extraction equilibrium curve with D2EHPA in the fourth stage, FIGURE 11 is a graph showing HFeC14 extraction equi-librium curve with TBP in the fourth stage, FIGURE 12 is a graph showing FeC14 extraction equi-librium curve with amine in the fourth stage, FIGURE 13 is a graph showing Fe3 ion back-extraction equilibrium curve in the fourth stage, FIGURE 14 i9 a graph showing HFeC14 and FeC14 back-extraction equilibrium curve in the fourth stage' FIGURE 15 is a graph showing V5+ ion extraction equi-librium curve in the fifth stage, FIGURE 16 is a graph showing the relation between V5 ion extraction and pH;
PIGURE 17 is a graph showing V5+ ion back-extraction equilibrium curve in the fi~th stage, FIGURE 18 is a graph showing the relation between H2S04 concentration and Fe ion extraction coefficient.
FIGURE 19 is a graph showing the relation between Mn +
and Fe2+ ions extraction coefficient and pH;
FIGURE 20 is a graph showing Fe + ion scrub equilibrium curve.
The following explanation is based on the experiments carried out by the inventors. The typical chemical analysis of ilmenite used commonly as a raw material of TiO2 is shown as follows:
Ti02 FeO Fe23 V25 MnO Cr23 MgO
54 20 26 60 14.20 0 16 0.40 0.07 1.03 53.13 19.11 22.95 0.1~ 0.94 0.03 0.92 ' Values in wt.%
This invention is concerned with the production of titanium dioxide which i9 characterized by recovery of reusable H2S04, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc. from FeS04.nH20 and waste acid of 20 - 4~/0 H2S04 containing abundant heavy metallic ions, which are by-produced in the production of TiO2 by dissolution of Ti raw mate-rial~ such as ilmenite, steel production slag, quch as electric furnace slag, convertor slag with H2S04.
In the conventional production o~ TiO2 using H2S04, the required 98% H2S04 per 1 ton of TiO2 product is 3.5 to 4.2 tons.
Nevertheless, the economical treatment of FeS04.nH20 and waste acid~ by-produced in abundance after the separation of Ti com-pounds by hydrolysis process has not been found and the allow-ance to stand or discard them as untreatment has given rise to serious pollution problems. This invention is originated to over-come the faults of the conventional production process described above.
The present invention relates to a production of ti-tanium dioxide which is characterized by recovery of reusable H2S04, high pure Fe oxide and hydroxide and fractional recovery of Mn, V and Cr, etc. from FeS04.nH20 and waste acid of 20 - 40YO
H2S04 containing abundant heavy metallic ions, which are by-pro-duced in the production of TiO2 by dissolutlon of Ti raw materials such as ilmenite, steel production slag, such as electric furnace slag, convertor slag w th H2S04.
The Qummary of this invention is as follows. The pre-sent invention iB firstly characterized with~ production of waste acids and FeS04.nH20 as follows. The aqueou~ solution pretreated after dissolution of Ti raw materials with H2S04 is brought into contact and mixed with an organic solvent (A) to extract metallic ions such as Cr3+ and Nb5+ ions in the first st~ge and the bulk of Ti ions in the resulting aqueous solution 10794~8 is separated by well-known hydrolysis process in the 2nd stage, The rnetallic ions such as Ti, Mn and V ions remaining in the re-sult:ing aqueous solution are extracted into an organic solvent (B) ln the 3rd stage, an organic solvent (C) extracts Fe ions in the resulting aqueous solution after the oxidation of Fe2+
ions to Fe ions in the 4th stage and V5+ ions in the resulting aqueous solution are extracted into an organic solvent (D) in the 5th stage, The resulting aqueous solution from the 5th stage is the reusable regenerated acid for dissolution of raw materials.
The 2nd characteristic OL present invention is con-cerned with the extraction of Fe ions from the aqueous solution using C12 gas for the oxidation as follows. After the conversion of Fe2+ ions in the aqueous solution from the 3rd stage to Fe3 ions using C12 gas, the amount of HCl required to extract Fe3 ions in the aqueous solution as Fe chloride complex is added to the resulting aqueous solution and is contacted with an organic solvent (E) to extract Fe-Cl ions into the organic phase, The 3rd characteristic of this invention is concerned with the reduction of energy in concentration process of acid as follows. FeS04.nH20 by-produced in the pretreatment process is dissolved with water or acids from the 4th stage, the oxidation of Fe + ions in the resulting aqueous solution to Fe ions is finished and then Fe3+ ions in the resulting aqueous solution are extracted into the organic phase with contact of the organic' solvent ~C). The increasing concentration of regenerated acid by several repetitions of the above operation in compliance with dema,nd yields the reduction of energy in the following concen-tration process of acid.
The 4th characteristic of present invention is con-cerned with the reasonable treatment of FeS04.nH20 with the fractional extraction of Mn and Fe ions as follows. After dis-solution of FeS04'nH20 by-produced with water, Mn + ions in the resulting aqueous solution are extracted with an organic solvent 10794~8 (F) into th~ organic phase to separate from ~e ions in the re-sulting aqueous solution, Fe2+ ions are oxidized to Fe3+ ions and then Fe3+ ions are extracted into the organic phase with contact of the organic solvent (C). The concentration of recovered acid is enhanced by several repetitions of the above operation in eom-pliance with demand and recycled for dissolution of raw materials by way of the eoncentration proeess The 5th charaeteristie of this invention is concerned with the reduetion of reeovery cost by rising Fe concentration in the aqueous solution introduced into the recovery process of HCl and Fe as follows. The Fe concentration of the aqueous solution introduced into the reeovery proeess of HCl and Fe is increased by extracting Fe3+ ions in the baek-extraction solution of the organie solvent (C) with eontaet of the organic solvent (E) and stripping with water. The inereased Fe eoneentration produees the reduetion of reeovery eost.
The 6th eharaeteristie of this invention is concerned with the reasonable recovery of Fe compounds using both solvent extraction and diaphragm-eleetrolysis teehniques as follows.
The baek-extraetion solution of the organie solvent (C) or of the organie-solvent (E) is introdueed into the eathode eompartment of diaphragm-eleetrolysis, Fe3+ ions are reduced to Fe ions there, free acid is transferred to the anode eompartment and hydrated Fe oxide or hydroxide is reeovered with eontaet of air or oxygen and the aqueous solution in the eathode eompartment eontaining a lesser amount of free reeovered aeid.
The 7th eharaeteristic of this invention is concerned with the fraetional reeovery of metallie ions eoextraeted into the organie solvent (B) as follows. Mn, V and Fe ions coextraeted`
into the organie solvent (B) are serubbed with HCl or H2S04, Ti ions in the organie solvent (B) is baek-extraeted into the aqueous solu-tion with eontaet of (NH4)2C03 + NH3 solution, and then the organie 1079~88 solvent converted from H type to N~I3 type in the above operationis ac~ain converted to H type with contact of H2S04. When Cr3 ions are coextracted, they in the organic phase can be recovered into the aqueous solution with contact of HCl ~ H202 or HCl +
NaCl solution. Thus, the individual metallic ion coextracted into the organic solvent (B) is fractionally recovered. When A13+ and Mg2 ions are accumulated in the recovered acid during recycle of recovered acid, the enhacement of their ions concen-tration is depressed by taking one part of them out of the extraction system and the solution taken out is recovered as (NH4)2S04 by neutralizing with NH3.
The invention relatec to a process for the prepara-tion of titanium dioxide by dissolving titanium-containing raw materials in ~ulphuric acid to form an aqueous solution of sulphuric acid containing dissolved titanium and other metals, separating ferrous sulphate from the aqueous solution and then isolating titanium as the desired titanium dioxide by the steps of:
a) where dissolved chromium and niobium are present in the aqueous solution, contacting the aqueous solution with an organic extractant ~A) capable of extracting chromium and niobium so as to extract the dissolved chromium and niobium from the a~ueous solution, b) hydrolysing the aqueous solution so as to precipitate the majority of dissolved titanium therefrom and subsequently recovering the precipitated titanium compound as titanium dioxide;
c) contacting the hydrolysed aqueous solution with an organic extractant (B) capable of extracting titanium from the aqueous solution for subsequent recovery as titanium dioxide:
~ -4-10~5~48~
d) oxidizing the thus-contacted aqueous solution to convert ferrous ions present therein -to ferric ions and contacting the oxidized aqueous solution with an organic extractant (c) capable of extracting ferric ions so as to extract ferric ions from the aqueous solution; and where dissolved vanadium is present in the aqueous solution;
e) contacting the resultant aqueous solution with an organic extractant (D) capable of extracting vanadium so as to extract dissolved vanadium from the aqueous solution to yield a liquor essentially comprising sulphuric acid substantially free from dissolved chromium, niobium, titanium, iron and vanadium.
- 4a -107948~
FIGURE 7 is a graph showing Ti ion extraction equi-librium curve in the third stage, FIGURE 8 is a graph showing Ti ion back-extraction equilibrium curve in the third stage' FIGURE 9 is a graph showing Cr3+ ion back-extraction equilibrium curve in the third stage, FIGURE 10 is a graph showing Fe3 ion extraction equilibrium curve with D2EHPA in the fourth stage, FIGURE 11 is a graph showing HFeC14 extraction equi-librium curve with TBP in the fourth stage, FIGURE 12 is a graph showing FeC14 extraction equi-librium curve with amine in the fourth stage, FIGURE 13 is a graph showing Fe3 ion back-extraction equilibrium curve in the fourth stage, FIGURE 14 i9 a graph showing HFeC14 and FeC14 back-extraction equilibrium curve in the fourth stage' FIGURE 15 is a graph showing V5+ ion extraction equi-librium curve in the fifth stage, FIGURE 16 is a graph showing the relation between V5 ion extraction and pH;
PIGURE 17 is a graph showing V5+ ion back-extraction equilibrium curve in the fi~th stage, FIGURE 18 is a graph showing the relation between H2S04 concentration and Fe ion extraction coefficient.
FIGURE 19 is a graph showing the relation between Mn +
and Fe2+ ions extraction coefficient and pH;
FIGURE 20 is a graph showing Fe + ion scrub equilibrium curve.
The following explanation is based on the experiments carried out by the inventors. The typical chemical analysis of ilmenite used commonly as a raw material of TiO2 is shown as follows:
Ti02 FeO Fe23 V25 MnO Cr23 MgO
54 20 26 60 14.20 0 16 0.40 0.07 1.03 53.13 19.11 22.95 0.1~ 0.94 0.03 0.92 ' Values in wt.%
2 to 2.5 tons of raw material described above per 1 ton of Ti02 product is sulfatized with 3.5 to 4 tons of 98% H2S04 After heating and dissolving, Fe3 ions in the resulting aqueous solution is completely reduced with Fe scrap. The clarified solu-tion is produced by removing undissolved residues. The chemical composition of the aqueous solution which is obtained after re-moving one part of Fe ions as FeS04 nH20 crystal is shown as fol-lows:
Ti02 Fe T H2S4 Cr Mn V Mg 200 32 300 0.1 1.8 0.3 1.6 Values in g/1 The synthesized solution having the above mentioned chemical composition and no Fe3+ ions was as a standard solution in the following experiment.
(1) The First Stage The extraction of Cr3+ and ~b5+ ions with the organic solvent (A) is run before hydrolysis process owing to their supe-rior extractability in lower concentration of free acid and higher temperature of the aqueous solution Organic solvent (A) is made up of primary, amine secondary, tertiary or quaternary amine, for example, "Primene JMT" (tradename, primary amine produced by R'ohm and Haas~, "Amberlite LA-l" (tradename, secondary amine produced by R~hm and Haas), "Alamine 336" (tradename, tertiary amine pro-duced by General Mills), and "Aliquat 336" (tradename, quar~ernary amine produced by General Mills), 2 - 5% higher alcohol such as octanol, dodecanol or isodecanol as a modifier and aromatic, ali-phatic or paraffin hydrocarbon as a diluent. The organic solvents used in this experiment indicate only one example and of course similar organic solvents can be utilized.
- Extraction -The extraction test is done with the increased concen-tration of Cr3+ and Nb5+ ions by adding and adjusting Cr2(S04)3 and NbC15 to the aqueous solution described above. Cr and Nb ions are extracted according to the under formulas.
Nb(S4)2 + H2RN + H ~ ( 2 ) Mb0(S04)2 (see Figure 3) (Aq) (Org) (Aq) (Org) CrS04 2RN ~ (H2RNH ) CrS04 (see Figure 4) (Aq) (Org) (Aq) (Org) The extraction of Cr3 ions is performed in the order of primary amine ~ secondary amine ~ tertiary amine. However, there is little difference in the extraction of Nb5+ ions with various amines. The main factors of Cr3 ions extraction are temperature, contact time and concentration of free acid. The high extractability of Cr3+ ions is obtained in 50 to 80& and longer contact time as higher concentration of free acid.
- Stripping -Cr3 ions extracted into the organic solvent (A) are stripped from the organic phase with contact of HC1 or H2S04 ac-cording to the under formula.
~H2R~H ) CrS04 + 1/2 H2S04~ 2 N + 1/2 Cr2(S04)3 + 2 H+
(Org) (Aq) (Org) (Aq) (Aq) Back-extraction test (see Figure 5) Temp. Back~extraction % Temp. Back-extraction %
15% HCl 20C 88.9% 20% H2S4 20C 81.4%
20% HCl 20C 99 . 0% 30/O H2S04 60C 98.~o Af~er removing Cr3 ions from the organic solvent (A), 5+
Nb ions is stripped from the organic phase with contact of ~H4F + ~H3`solution according to the following formula.
10~7~488 (H2R~I ) NbO(S04)2 + NII4F + 4N~I40M
(Org) (Aq) (Aq) M2RN~Nb(O~I)5+2(NII4)2S04+NI-I4F
(Org) (ppt) (Aq) (Aq) (2) The Secon~. Stage A large amount of Ti ions is removed as Ti hydroxide by hydrolysis process of the resulting aqueous solution which Cr3+
and Nb5+ ions are extracted off. The approximate chemical com-position of the liquor after separation of titanium is shown as follows.
TiO2 Fe2+ 2 4 Cr3+ V4+ Mn2+ Mg2+
7 32 300 Tr 0.3 2.8 1.6 Values in g/l
Ti02 Fe T H2S4 Cr Mn V Mg 200 32 300 0.1 1.8 0.3 1.6 Values in g/1 The synthesized solution having the above mentioned chemical composition and no Fe3+ ions was as a standard solution in the following experiment.
(1) The First Stage The extraction of Cr3+ and ~b5+ ions with the organic solvent (A) is run before hydrolysis process owing to their supe-rior extractability in lower concentration of free acid and higher temperature of the aqueous solution Organic solvent (A) is made up of primary, amine secondary, tertiary or quaternary amine, for example, "Primene JMT" (tradename, primary amine produced by R'ohm and Haas~, "Amberlite LA-l" (tradename, secondary amine produced by R~hm and Haas), "Alamine 336" (tradename, tertiary amine pro-duced by General Mills), and "Aliquat 336" (tradename, quar~ernary amine produced by General Mills), 2 - 5% higher alcohol such as octanol, dodecanol or isodecanol as a modifier and aromatic, ali-phatic or paraffin hydrocarbon as a diluent. The organic solvents used in this experiment indicate only one example and of course similar organic solvents can be utilized.
- Extraction -The extraction test is done with the increased concen-tration of Cr3+ and Nb5+ ions by adding and adjusting Cr2(S04)3 and NbC15 to the aqueous solution described above. Cr and Nb ions are extracted according to the under formulas.
Nb(S4)2 + H2RN + H ~ ( 2 ) Mb0(S04)2 (see Figure 3) (Aq) (Org) (Aq) (Org) CrS04 2RN ~ (H2RNH ) CrS04 (see Figure 4) (Aq) (Org) (Aq) (Org) The extraction of Cr3 ions is performed in the order of primary amine ~ secondary amine ~ tertiary amine. However, there is little difference in the extraction of Nb5+ ions with various amines. The main factors of Cr3 ions extraction are temperature, contact time and concentration of free acid. The high extractability of Cr3+ ions is obtained in 50 to 80& and longer contact time as higher concentration of free acid.
- Stripping -Cr3 ions extracted into the organic solvent (A) are stripped from the organic phase with contact of HC1 or H2S04 ac-cording to the under formula.
~H2R~H ) CrS04 + 1/2 H2S04~ 2 N + 1/2 Cr2(S04)3 + 2 H+
(Org) (Aq) (Org) (Aq) (Aq) Back-extraction test (see Figure 5) Temp. Back~extraction % Temp. Back-extraction %
15% HCl 20C 88.9% 20% H2S4 20C 81.4%
20% HCl 20C 99 . 0% 30/O H2S04 60C 98.~o Af~er removing Cr3 ions from the organic solvent (A), 5+
Nb ions is stripped from the organic phase with contact of ~H4F + ~H3`solution according to the following formula.
10~7~488 (H2R~I ) NbO(S04)2 + NII4F + 4N~I40M
(Org) (Aq) (Aq) M2RN~Nb(O~I)5+2(NII4)2S04+NI-I4F
(Org) (ppt) (Aq) (Aq) (2) The Secon~. Stage A large amount of Ti ions is removed as Ti hydroxide by hydrolysis process of the resulting aqueous solution which Cr3+
and Nb5+ ions are extracted off. The approximate chemical com-position of the liquor after separation of titanium is shown as follows.
TiO2 Fe2+ 2 4 Cr3+ V4+ Mn2+ Mg2+
7 32 300 Tr 0.3 2.8 1.6 Values in g/l
(3) The Third Stage Ti ions and one part of V4+ ions in the resulting aqueous solution are extracted into the organic phase with the organic solvent (B). When there are Cr3 ions with omitting the first stage, Cr ions are coextracted with Ti ions into the or-ganic solvent (B) as shown in Figure 6. The organic solvent (B) is composed of alkyl phosphoric acid, for example, D2EHPA(Di-2-ethyl hexyl phosphoric acid) and H2DDP (Mono-dodecyl phosphoric acid), 2 - 5% higher alcohol such as octanol, decanol or isbdeca-nol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent.
- Extraction -Ti4+ ions are extracted with the organic solvent (B) according to the under formula.
1~:)794~8 Ti ~ 4 [(R0)2POOI-I) ~ Ti ((R0)2P00)4 + 4 I-I (see Figure 7) (~q) (Org) (Org) (Aq) The resulting solution includes a small amount of V5+
ions and they are slightly extracted, While, Fe3+ ions are not commonly contained in the resulting solution, but if Fe3+ ions exist in it, they are completely extracted like Ti4+ ions. Mn ions are extracted as the concentration of free acid lowers.
- Continuous extraction test -The liquor as shown in the under table was continuous-ly treated with the organic solvent (B) at the flow rate o~ 0.15 l/min. using a mixer settler (100 mm W x 500 mm L x 180 mm H), The mixer was of the pump~suction type and rotated at 120 - 310 r,p,m, depending on the interface level in the settler using a non-stepwise speed changer. The organic solvent used consists of 200/o D2EHPA, 3% octanol and kerosene in balance.
The third stage - Extraction Flow ratio Inlet (Aq) Outlet(Aq) Appara- 0/A Ti V Fe H2S04 T~ V Fe H2S04 5 Stage 1.0/ 7.1 0,2 31.8 300 tr 0.18 31.8 300 mixer- 1.0 settler - Outlet (Org) Solvent Ti V Fe H2S04 200/oD2EHPA
7,1 0.02<0.0l <0.1 3% octanol diluted with kerosene Values in g/l - Scrubbing -V4+, Fe3+ and Mn + ions, which are extracted in the low concentration of free acid, coextracted with Ti4+ ions into the organic solvent (B) are scrubbed from the organic solvent (B) _ 9 _ :. - , ;
with contact Of lICl, II2SO~ or ~03, but Ti and cr ions are not scrubbed.
Scrubbing test with 15% HCl Metallic ions Flow ratio Temp, shaking Back-concentration 0/a time extraction %
in the org.phase Mn2+ 0,2 g/l 1.0 Room temp, 15 min, 99,5%
V4++ 0'5 g/l 1.0 " " 99.0~/O
Fe3 1,0 g/l " " " 98,5%
Cr3+ 0,5 g/l " 60C 30 min, 0 %
Ti4 7'0 g/l " Room temp, " 0 %
The organic solvent (B) extracted Ti ions is scrubbed with contact of HCl, H2S04 or HN03 to remove V and Mn ions, etc, coextracted with Ti ions into the organic solvent (B).
The selection of HCl, H2S04 or HN03 as a scrub solution is done after consideration of the finished recovery form of V and Mn, etc, scrubbed, The organic solvent (B) after the scrubbing pro-cess includes only Ti ions, but includes also Cr ions provided that the first stage is omitted, - Continuous scrubbing test -The apparatus for test is the same one used for the extraction process and the flow rates of organic aqueous phases are 0,5 l/min, and 0.05 l/min. respectively, The third stage - Scrubbing Appara- Flow ratio Inlet(Org) Outlet(Org) Outlet(Aq) tus 0/A Ti V Ti V Ti V
5 Stage mixer- 10/1 7,10 0,02 7,10 0,01 - 0,2 settler Values in g/l Note: Temp,: 35 C Scrub sol, : 15% HCl - Stripping -Ti4+ ions in the organic solvent (B) after the scrub-bing process are stripped in the following stripping process, Back-extraction test of Ti ions with various back-extraction solutions Flow ratio : O/A = 1/1, Shaking time: 15 min. Temp.
: Room temp.
Back-extraction % Back-extraction %
6N H2S4 0.5 N HF 64,71 12N H2S4 0.5N NH4F 75.03 6N HCl o N 2 4 % 2 2 36.04 12N HCl o (NH4)2 4 10 4N HN03 (NH4)2S04 + NH3 98 0 8N HN03 0.4 Saturated (NH4)2C03 99.5 llN H3P04 5.7 IM (NH4)2Co3 + N 3 99.S
It is considered from the result of back-extraction test that 0.5 M - saturated (NH4)2C03 + NH3 solutions maintained between 7 and 9.5 of pH values and over 2 M(NH4)2S04 + NH3 solu-tions maintained over 7.0 of pH values are the most suitable back-extraction solutions of Ti ions in the standpoint of cost and sub-sequent operations. Therefore, the mechanism of the back-extrac-tion of Ti ions is shown as follows.
~(R0)2P~4 + 2(NH4)2C03 + 4 NH40H ~ Ti(OH)4 +
(Org) (A~) (Aq) (ppt)
- Extraction -Ti4+ ions are extracted with the organic solvent (B) according to the under formula.
1~:)794~8 Ti ~ 4 [(R0)2POOI-I) ~ Ti ((R0)2P00)4 + 4 I-I (see Figure 7) (~q) (Org) (Org) (Aq) The resulting solution includes a small amount of V5+
ions and they are slightly extracted, While, Fe3+ ions are not commonly contained in the resulting solution, but if Fe3+ ions exist in it, they are completely extracted like Ti4+ ions. Mn ions are extracted as the concentration of free acid lowers.
- Continuous extraction test -The liquor as shown in the under table was continuous-ly treated with the organic solvent (B) at the flow rate o~ 0.15 l/min. using a mixer settler (100 mm W x 500 mm L x 180 mm H), The mixer was of the pump~suction type and rotated at 120 - 310 r,p,m, depending on the interface level in the settler using a non-stepwise speed changer. The organic solvent used consists of 200/o D2EHPA, 3% octanol and kerosene in balance.
The third stage - Extraction Flow ratio Inlet (Aq) Outlet(Aq) Appara- 0/A Ti V Fe H2S04 T~ V Fe H2S04 5 Stage 1.0/ 7.1 0,2 31.8 300 tr 0.18 31.8 300 mixer- 1.0 settler - Outlet (Org) Solvent Ti V Fe H2S04 200/oD2EHPA
7,1 0.02<0.0l <0.1 3% octanol diluted with kerosene Values in g/l - Scrubbing -V4+, Fe3+ and Mn + ions, which are extracted in the low concentration of free acid, coextracted with Ti4+ ions into the organic solvent (B) are scrubbed from the organic solvent (B) _ 9 _ :. - , ;
with contact Of lICl, II2SO~ or ~03, but Ti and cr ions are not scrubbed.
Scrubbing test with 15% HCl Metallic ions Flow ratio Temp, shaking Back-concentration 0/a time extraction %
in the org.phase Mn2+ 0,2 g/l 1.0 Room temp, 15 min, 99,5%
V4++ 0'5 g/l 1.0 " " 99.0~/O
Fe3 1,0 g/l " " " 98,5%
Cr3+ 0,5 g/l " 60C 30 min, 0 %
Ti4 7'0 g/l " Room temp, " 0 %
The organic solvent (B) extracted Ti ions is scrubbed with contact of HCl, H2S04 or HN03 to remove V and Mn ions, etc, coextracted with Ti ions into the organic solvent (B).
The selection of HCl, H2S04 or HN03 as a scrub solution is done after consideration of the finished recovery form of V and Mn, etc, scrubbed, The organic solvent (B) after the scrubbing pro-cess includes only Ti ions, but includes also Cr ions provided that the first stage is omitted, - Continuous scrubbing test -The apparatus for test is the same one used for the extraction process and the flow rates of organic aqueous phases are 0,5 l/min, and 0.05 l/min. respectively, The third stage - Scrubbing Appara- Flow ratio Inlet(Org) Outlet(Org) Outlet(Aq) tus 0/A Ti V Ti V Ti V
5 Stage mixer- 10/1 7,10 0,02 7,10 0,01 - 0,2 settler Values in g/l Note: Temp,: 35 C Scrub sol, : 15% HCl - Stripping -Ti4+ ions in the organic solvent (B) after the scrub-bing process are stripped in the following stripping process, Back-extraction test of Ti ions with various back-extraction solutions Flow ratio : O/A = 1/1, Shaking time: 15 min. Temp.
: Room temp.
Back-extraction % Back-extraction %
6N H2S4 0.5 N HF 64,71 12N H2S4 0.5N NH4F 75.03 6N HCl o N 2 4 % 2 2 36.04 12N HCl o (NH4)2 4 10 4N HN03 (NH4)2S04 + NH3 98 0 8N HN03 0.4 Saturated (NH4)2C03 99.5 llN H3P04 5.7 IM (NH4)2Co3 + N 3 99.S
It is considered from the result of back-extraction test that 0.5 M - saturated (NH4)2C03 + NH3 solutions maintained between 7 and 9.5 of pH values and over 2 M(NH4)2S04 + NH3 solu-tions maintained over 7.0 of pH values are the most suitable back-extraction solutions of Ti ions in the standpoint of cost and sub-sequent operations. Therefore, the mechanism of the back-extrac-tion of Ti ions is shown as follows.
~(R0)2P~4 + 2(NH4)2C03 + 4 NH40H ~ Ti(OH)4 +
(Org) (A~) (Aq) (ppt)
4 ~(R0)2 4~ ( 4)2 3 (see Figure 8) (Org) (Aq) As shown in~the above formula, (NH4)2C03 used for the back-extraction forms~ee ion in the back-extraction of Ti and HC03 ion formed reacts with NH3 to form (NH4)2C03 again.
The third stage - Stripping Appara- Flow ratio Inlet(Org) Outlet(Org) Outlet(Aq) tus 0/A Ti Ti Ti
The third stage - Stripping Appara- Flow ratio Inlet(Org) Outlet(Org) Outlet(Aq) tus 0/A Ti Ti Ti
5 Stage-mixer- 1/1 7.10 0.01 7.10*
settler ( H4)2C03 + NH3 pH- 9.5 Temp.: 23C
1079~813 Remark: The value of Ti* in the back-extraction solution is one obtained in remelting the precipitate as Ti(OH)4. As the organic solvent ( B ) becomes NH4 type by stripping Ti ions, it is converted to H type with contact of H2S04 or HCl in the following process. When Cr3+ ions are coextracted, Cr3+
ions are stripped with contact of H2S04 + H202, HCl + H202 or HCl + NaCl solution and then NH4 type of the organic solvent (B) is converted to H type (see Figure 9).
(4) The Fourth Stage - Extraction -Fe2+ ions in the resulting solution which Ti ions are separated are converted to Fe3 ions with H202, oxygen, high pres-sure air or electro-oxidation and Fe3+ ions in the resulting aqueous solution are extracted into the organic phase with the organic solvent (C). The organic solvent (C) is composed of alkyl phosphoric acid, for example, D2EHPA, mixed solvent of alkyl phos-phoric acid and LlX-63 (tradename, chelate reagent produced by General Mills) or ~-bromo lauric acid, 2-5% higher alcohol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent.
The extraction mechanism of Fe3+ ion with alkyl phos-phoric acid is shown as follows. (See Figure 10) Fe + 3 ~(RO)2P00H) = Fe ~(R0)2P00~3 + 3 H*
(Aq) (Org) (Org) (Aq) While, Fe2+ ions are oxidized to Fe3+ ions using C12 gas and Fe ions are extracted into the organic phase with the organic solvent tE) after adding HCl to the resulting aqueous solution in an amount enough to extract Fe ions as Fe chloride compl~x. The organic solvent (E) is made up of phosphoric acid ester, for exam-ple, TBP (tri-butyl phosphoric acid), TOP (tri-octyl phosphoric acid), DBBP (di-butyl butyl phosphonate) or TOP0 (tri-octyl phos-phine oxide) and aromatic, aliphatic or paraffin hydrocarbon as a ~079488 diluent. Moreover, the oryanic solvent (E) may be made up of pri-mary, secondary, tertiary or quarternary amine, higher alcohol as a modifier and aromatic, aliphatic, or paraffin hydrocarbon as a diluent The test used Primene-JMT as a primary amine, LA-l as a secon~ary amine, Alamine 336 as a tertiary amine and Aliquat 336 as a quarternary amine. Of course, similar amines can be utilized besides the amines described above. Furthermore, mixed solvent of phosphoric acid ester such as TBP and tertiary amine such as TOA
(tri-octyl amine) can be used. Fe ions are extracted into the organic phase with phosphoric acid ester or amine according to the under formulas.
FeC13 + H + Cl + 2TBP ~ HFeC14 2TBP (Extraction by TBP.
(Aq) (Aq)(Aq) (Org) (Org) see Fig 12) FeC14 + (R3NH) ~ (R NH+) FeCl~ (Extraction by tertiary (Aq) (Org) (Org) amine. see Fig, 12) - Stripping -Fe3+ ions extracted into the organic phase with the organic solvent (C) are stripped from the organic phase with HCl and the organic solvent (C) is regenerated as shown in the fol-lowing formula.
Fe ~(R0)2P00)3 + 3HCl ~ FeC13+ 3~(R)2PooH) (see Fig 13) (Org) (Aq) (Aq) (Org) While, Fe chloride complex extracted into the organic phase with the organic solvent (E) is stripped from the organic phase with water and the organic solvent (E) is regenerated accord-ing to the under formulas (see Fig. 14).
HFeC14 2TBP + H20 ~ FeC13 + HCl + TBP
(Org) (Aq) (Aq) (Aq) (Org) (R3NH ) FeC14 + H20 ~ FeC13 + HCl + R3N
(Org) (Aq) (Aq) (Aq) (Org) - Continuous extraction and stripping test -, 107~488 The apparatus used for test is the same one used in ~he first stage Flow rate of organic and aqueous phases were 0.1 l/min.
Extraction Appara- Flow ratio Inlet(Aq) Outlet(Aq) Outlet(Org) tus 0/A Fe H2S4 Fe H2 4 Fe H2S04 10 Stage 3/1 31 8 300 ~0.01 300 10.6 ~ 0.01 mixer-settler 15 Stage mixer- 4/1 31.8 300 ~0 01 300 7 94 ~0 01 settler Note: 30~/O D2EHPA 3% decanol kerosene 15% TBP kerosene values in g/l Stripping Appara- Flow ratio Inlet(Org) Outlet~Org) Outlet(Aq) tus 0/A Fe HC1 Fe HC1 Fe HCl 10 Stage 1,5/1.0 10.6 - 0.1 - 15.9 150 mixer-settler " 10/1 7.94 20.5 0.6 1.5 73.4 189 Note: Room Temp. 150 g/l ~Cl 60 & H20 values in g/l (5) The Fifth Stage - Extraction -The resulting aqueous solution extracted off Fe ionscontains a small amount of Al , Mg , Mn and V ions and is reused for dissolution of Ti raw materials through the concentra-tion process. ~owever, since these metallic ions are gradually ~0 accumulated in recycling process, it is necessary to take them out of the system and to prevent their accumulation. When acid is taken out of the system or is recycled to reuse, it is-connec_-ed with the improved economization of the apparatus to extract and recover V4+ ions having economical value among them.
In the case of recycling to reuse, V0(S04)2 ions in the resulting aqueous solution which has no Fe ions and 300 - 500 g/l 1079~88 of free acid are extracted into the organic phase with contact of the organic solvent (D) (see Fig. 15). In the other case of takirly acid out the system, V03 ions in the aquous solution, which pll values are maintained between 2 and 4 with NH3, are extracted into the organic phase with contact of the organic solvent (D).
Fig 16 shows the relation between pH and V extraction coefficient.
The organic solvent (D) is made up of primary, secondary, tertiary or quarternary amine, 2 - 5% higher alcohol such as oc-tanol, decanol or isodecanol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent The amines used for test are Primene- JMT as a primary amine, LA-l as a secondary amine, Alamine 381 (tri isooctylamine produced by Ashland Chemical Co.) as a tertiary amine and Aliquat 336 as a quarternary amine. Of course, various similar amines can be commonly utilized besides the amines mentioned above.
- Stripping -VO(S04)2 ions extracted into the organic solvent (D) are stripped from the organic phase with contact of (NH4)2S04, While, V03 ions extracted into the organic solvent (D) can be stripped with NH4Cl + NE3 (see Fig, 17). Both V ions are recovered as the form of NX4V03.
settler ( H4)2C03 + NH3 pH- 9.5 Temp.: 23C
1079~813 Remark: The value of Ti* in the back-extraction solution is one obtained in remelting the precipitate as Ti(OH)4. As the organic solvent ( B ) becomes NH4 type by stripping Ti ions, it is converted to H type with contact of H2S04 or HCl in the following process. When Cr3+ ions are coextracted, Cr3+
ions are stripped with contact of H2S04 + H202, HCl + H202 or HCl + NaCl solution and then NH4 type of the organic solvent (B) is converted to H type (see Figure 9).
(4) The Fourth Stage - Extraction -Fe2+ ions in the resulting solution which Ti ions are separated are converted to Fe3 ions with H202, oxygen, high pres-sure air or electro-oxidation and Fe3+ ions in the resulting aqueous solution are extracted into the organic phase with the organic solvent (C). The organic solvent (C) is composed of alkyl phosphoric acid, for example, D2EHPA, mixed solvent of alkyl phos-phoric acid and LlX-63 (tradename, chelate reagent produced by General Mills) or ~-bromo lauric acid, 2-5% higher alcohol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent.
The extraction mechanism of Fe3+ ion with alkyl phos-phoric acid is shown as follows. (See Figure 10) Fe + 3 ~(RO)2P00H) = Fe ~(R0)2P00~3 + 3 H*
(Aq) (Org) (Org) (Aq) While, Fe2+ ions are oxidized to Fe3+ ions using C12 gas and Fe ions are extracted into the organic phase with the organic solvent tE) after adding HCl to the resulting aqueous solution in an amount enough to extract Fe ions as Fe chloride compl~x. The organic solvent (E) is made up of phosphoric acid ester, for exam-ple, TBP (tri-butyl phosphoric acid), TOP (tri-octyl phosphoric acid), DBBP (di-butyl butyl phosphonate) or TOP0 (tri-octyl phos-phine oxide) and aromatic, aliphatic or paraffin hydrocarbon as a ~079488 diluent. Moreover, the oryanic solvent (E) may be made up of pri-mary, secondary, tertiary or quarternary amine, higher alcohol as a modifier and aromatic, aliphatic, or paraffin hydrocarbon as a diluent The test used Primene-JMT as a primary amine, LA-l as a secon~ary amine, Alamine 336 as a tertiary amine and Aliquat 336 as a quarternary amine. Of course, similar amines can be utilized besides the amines described above. Furthermore, mixed solvent of phosphoric acid ester such as TBP and tertiary amine such as TOA
(tri-octyl amine) can be used. Fe ions are extracted into the organic phase with phosphoric acid ester or amine according to the under formulas.
FeC13 + H + Cl + 2TBP ~ HFeC14 2TBP (Extraction by TBP.
(Aq) (Aq)(Aq) (Org) (Org) see Fig 12) FeC14 + (R3NH) ~ (R NH+) FeCl~ (Extraction by tertiary (Aq) (Org) (Org) amine. see Fig, 12) - Stripping -Fe3+ ions extracted into the organic phase with the organic solvent (C) are stripped from the organic phase with HCl and the organic solvent (C) is regenerated as shown in the fol-lowing formula.
Fe ~(R0)2P00)3 + 3HCl ~ FeC13+ 3~(R)2PooH) (see Fig 13) (Org) (Aq) (Aq) (Org) While, Fe chloride complex extracted into the organic phase with the organic solvent (E) is stripped from the organic phase with water and the organic solvent (E) is regenerated accord-ing to the under formulas (see Fig. 14).
HFeC14 2TBP + H20 ~ FeC13 + HCl + TBP
(Org) (Aq) (Aq) (Aq) (Org) (R3NH ) FeC14 + H20 ~ FeC13 + HCl + R3N
(Org) (Aq) (Aq) (Aq) (Org) - Continuous extraction and stripping test -, 107~488 The apparatus used for test is the same one used in ~he first stage Flow rate of organic and aqueous phases were 0.1 l/min.
Extraction Appara- Flow ratio Inlet(Aq) Outlet(Aq) Outlet(Org) tus 0/A Fe H2S4 Fe H2 4 Fe H2S04 10 Stage 3/1 31 8 300 ~0.01 300 10.6 ~ 0.01 mixer-settler 15 Stage mixer- 4/1 31.8 300 ~0 01 300 7 94 ~0 01 settler Note: 30~/O D2EHPA 3% decanol kerosene 15% TBP kerosene values in g/l Stripping Appara- Flow ratio Inlet(Org) Outlet~Org) Outlet(Aq) tus 0/A Fe HC1 Fe HC1 Fe HCl 10 Stage 1,5/1.0 10.6 - 0.1 - 15.9 150 mixer-settler " 10/1 7.94 20.5 0.6 1.5 73.4 189 Note: Room Temp. 150 g/l ~Cl 60 & H20 values in g/l (5) The Fifth Stage - Extraction -The resulting aqueous solution extracted off Fe ionscontains a small amount of Al , Mg , Mn and V ions and is reused for dissolution of Ti raw materials through the concentra-tion process. ~owever, since these metallic ions are gradually ~0 accumulated in recycling process, it is necessary to take them out of the system and to prevent their accumulation. When acid is taken out of the system or is recycled to reuse, it is-connec_-ed with the improved economization of the apparatus to extract and recover V4+ ions having economical value among them.
In the case of recycling to reuse, V0(S04)2 ions in the resulting aqueous solution which has no Fe ions and 300 - 500 g/l 1079~88 of free acid are extracted into the organic phase with contact of the organic solvent (D) (see Fig. 15). In the other case of takirly acid out the system, V03 ions in the aquous solution, which pll values are maintained between 2 and 4 with NH3, are extracted into the organic phase with contact of the organic solvent (D).
Fig 16 shows the relation between pH and V extraction coefficient.
The organic solvent (D) is made up of primary, secondary, tertiary or quarternary amine, 2 - 5% higher alcohol such as oc-tanol, decanol or isodecanol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent The amines used for test are Primene- JMT as a primary amine, LA-l as a secondary amine, Alamine 381 (tri isooctylamine produced by Ashland Chemical Co.) as a tertiary amine and Aliquat 336 as a quarternary amine. Of course, various similar amines can be commonly utilized besides the amines mentioned above.
- Stripping -VO(S04)2 ions extracted into the organic solvent (D) are stripped from the organic phase with contact of (NH4)2S04, While, V03 ions extracted into the organic solvent (D) can be stripped with NH4Cl + NE3 (see Fig, 17). Both V ions are recovered as the form of NX4V03.
(6) The Treatment of By~product FeS04 nH20 The H2S04 concentration produced after the extraction of Fe3+ ions and almost all heavy metallic ions in the fourth stage is 250 - 300 g/l and consequently this low concentration of H2S04 en- '!
hances the energy cost of concentration to reuse for the dissolu-tion of raw materials through the concentration process. The H2S04 concentration if increased by dissolving FeS04'nH20 by-produced in the pretreatment process into the aqueous solution removed Fe3 ions in order to reduce this energy cost. The several repetitions of the above operation in compliance of demand can diminish the energy cost of concentration. The relation between H2S04 concen-tration and Fe ions extraction coe~icient is shown in Fig, 18.
FeS04 nH20 often includes MnS04. As shown in the flow-sheet of Fig. 2~ Mn ions are separated from Fe ions by ex-tracting Mn ions with contact of the organic solvent (F) in the lower concentration of free acid produced by the dissolution of FeS04 nH20 crystal with water (see Fig l9).
The organic solvent (F) is composed of alkyl phosphoric acid, for example, D2EHPA~ H2DDP, 2 - 5% higher alcohol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent. While, the organic solvent (F) may be made up of mixed solvent of D2EHPA and LLX-63 or primary, secondary, tertiary or quarternary amine. As described above, the mixed solvents con-sisted of mainly alkyl phosphoric acid and 5 - 20~/o of LIX.-63 or ~-bromo lauric acid are used to extract Mn ions.
A small amount of Fe2+ ions coextracted with Mn ions are scrubbed from the organic solvent (F) with contact of MnS04 solution having 2 ~ 3,5 of pH values, the organic solvent (F) contains only Mn ions and consequently Mn ions are stripped from the organic solvent (F) with 300 g of H2S04 in the follow-ing process.
- Continuous extraction test -Continuous extraction test using the under-tabulated - FeS04 nH20 by-produced by H2S04 process was done and MnS04 was added to the resulting solution in order to facilitate the con-firmation of Mn extraction, Chemical analysis of FeS04'nH20 FeO TiO2 MnO
24.96% 0.22% 0.06%
pH value in dissolving 250 g of the above crystal with l liter of water was 1.8 and the chemical composition of the re-sulting solution to which Mn was added was shown as follows.
~ 16 -: :; ` ` :
Total II2S04 Fe Mn Ti (values in g/l) 90,7 48,8 2,0 0.3 Extraction Flow ratio Inlet(Aq) Outlet(Aq) Outlet(Org) 0/~ Fe Mn Ti Fe Mn Ti Fe Mn Ti Apparatus 10 Stage 4/1 48.8 2,0 0,3 48~4 0.1 Tr 0.1 0.49 0.1 mixer-settler " 2/1 48,8 2,0 0,3 48,6 0.1 Tr Tr 1.0 0.15 Note: 2 OD/o D2EHPA 10% LIX 6 3+10% D2EHPA
(values in g~
Fe + ions are coextracted with Mn + ions from pH values between 3, 5 and 3.8. In this case, Fe + ions extracted into the organic phase are scrubbed from the organic solvent (F) with MnS04 solution having 2 - 2.5 of pH value and the concentration of Mn in the MnS04 solution depends on the concentration of the or-ganic solvent (F). (see Fig. 20) Stripping Flow ratioInlet(Org) Outlet(Org) Outlet(Aq) 0/A Fe Mn Ti Fe Mn Ti Fe Mn Ti ,~-, Apparatus , 5 Stage10/1 0.10.49 Ool ~ 0,06 0,06~ 4.~ - 300g/1 mixer- H S0 settler - 2 4 - " 10/1 Tr 1.0 0~15 ~ 0~01 0~15~ 9~9 (values in g/l) Ti ions in the organic solvent (F) are not stripped and the organic solvent (F) is recycled. Since Ti concentration gra-dually increases, one part of the organic solvent (F) is taken outof the system and Ti ions in it are stripped from the organic ,phase with contact of (~H4)2C03 + ~H40H solution.
, . . .
10~9488
hances the energy cost of concentration to reuse for the dissolu-tion of raw materials through the concentration process. The H2S04 concentration if increased by dissolving FeS04'nH20 by-produced in the pretreatment process into the aqueous solution removed Fe3 ions in order to reduce this energy cost. The several repetitions of the above operation in compliance of demand can diminish the energy cost of concentration. The relation between H2S04 concen-tration and Fe ions extraction coe~icient is shown in Fig, 18.
FeS04 nH20 often includes MnS04. As shown in the flow-sheet of Fig. 2~ Mn ions are separated from Fe ions by ex-tracting Mn ions with contact of the organic solvent (F) in the lower concentration of free acid produced by the dissolution of FeS04 nH20 crystal with water (see Fig l9).
The organic solvent (F) is composed of alkyl phosphoric acid, for example, D2EHPA~ H2DDP, 2 - 5% higher alcohol as a modifier and aromatic, aliphatic or paraffin hydrocarbon as a diluent. While, the organic solvent (F) may be made up of mixed solvent of D2EHPA and LLX-63 or primary, secondary, tertiary or quarternary amine. As described above, the mixed solvents con-sisted of mainly alkyl phosphoric acid and 5 - 20~/o of LIX.-63 or ~-bromo lauric acid are used to extract Mn ions.
A small amount of Fe2+ ions coextracted with Mn ions are scrubbed from the organic solvent (F) with contact of MnS04 solution having 2 ~ 3,5 of pH values, the organic solvent (F) contains only Mn ions and consequently Mn ions are stripped from the organic solvent (F) with 300 g of H2S04 in the follow-ing process.
- Continuous extraction test -Continuous extraction test using the under-tabulated - FeS04 nH20 by-produced by H2S04 process was done and MnS04 was added to the resulting solution in order to facilitate the con-firmation of Mn extraction, Chemical analysis of FeS04'nH20 FeO TiO2 MnO
24.96% 0.22% 0.06%
pH value in dissolving 250 g of the above crystal with l liter of water was 1.8 and the chemical composition of the re-sulting solution to which Mn was added was shown as follows.
~ 16 -: :; ` ` :
Total II2S04 Fe Mn Ti (values in g/l) 90,7 48,8 2,0 0.3 Extraction Flow ratio Inlet(Aq) Outlet(Aq) Outlet(Org) 0/~ Fe Mn Ti Fe Mn Ti Fe Mn Ti Apparatus 10 Stage 4/1 48.8 2,0 0,3 48~4 0.1 Tr 0.1 0.49 0.1 mixer-settler " 2/1 48,8 2,0 0,3 48,6 0.1 Tr Tr 1.0 0.15 Note: 2 OD/o D2EHPA 10% LIX 6 3+10% D2EHPA
(values in g~
Fe + ions are coextracted with Mn + ions from pH values between 3, 5 and 3.8. In this case, Fe + ions extracted into the organic phase are scrubbed from the organic solvent (F) with MnS04 solution having 2 - 2.5 of pH value and the concentration of Mn in the MnS04 solution depends on the concentration of the or-ganic solvent (F). (see Fig. 20) Stripping Flow ratioInlet(Org) Outlet(Org) Outlet(Aq) 0/A Fe Mn Ti Fe Mn Ti Fe Mn Ti ,~-, Apparatus , 5 Stage10/1 0.10.49 Ool ~ 0,06 0,06~ 4.~ - 300g/1 mixer- H S0 settler - 2 4 - " 10/1 Tr 1.0 0~15 ~ 0~01 0~15~ 9~9 (values in g/l) Ti ions in the organic solvent (F) are not stripped and the organic solvent (F) is recycled. Since Ti concentration gra-dually increases, one part of the organic solvent (F) is taken outof the system and Ti ions in it are stripped from the organic ,phase with contact of (~H4)2C03 + ~H40H solution.
, . . .
10~9488
(7) The Recovery of HCl by Diaphragm - Electrolysis ~ s the concentration of Fe3+ ions in the back-extrac-tion solution of the organic solvent (C) including Fe3+ ions is im-possible to be increased as shown in Fiy. 13, the introduction of the above back-extraction solution into the apparatus of HCl re-covery by thermal-decomposition process enhances the energy cost of recovery and consequently the back-extraction solution is in-troduced into the cathode compartment of diaphragm-electrolysis, and free HCl produced there by the reduction of FeCl3 to FeCl2 is transferred to the anode compartment and recovered, - Continuous electrolysis test -The back-extraction solution of the organic solvent (C) is.fed into the cathode compartment by quantitative pump and the aqueous solution of low HCl concentration, which is the back-extraction solution of the organic solvent (C) and contains no Fe ions, is fed into the anode compartment, Electrolysis condition ~/~JOr~
. ~ Material of diaphragm : Film of Tetra-~e ethylene Thickness of " : 0.103 mm Void percent " : 55%
Hole diameter " : 0.3~
Water permeability " : 0,48 ml/cm H
Electric resistance : 0.1~ -cm Anod`e : carbon Cathode : Ti (Pt plating) Volume of anode or cathode room : 5 1 Temperature : 24 - 55C
Current densi~y : 2 A/dm - Continuous test at s-teady state -Cathode roorn Anode room Inlet Outlet InletOutlet Fe3 (g/l) 18.0 0.4 0 F 2+ ( " ) 21.0 0 HCl ~ " ) 176 27.4 50 178.0 vqolume(llH) . 5.7 The following diaphragms besides the above one were10 used, Electric Hole Void Water permeability Material resistance dia. %
Acetic 0.05-0.19~2-cm 0.1-0.4~ 58-62%0,11-0,3 ml/cm H
cellose Polypropy- 0,12-0,27 " 0.2-0.4~ 38-45% 0.02-0.2 "
lene Ion exchange 1.7 -3.2 " Water content : 38% , membrane The back-extraction solution of the organic solvent ~E) is the concentrated solution containing 75 - 85 g/l of Fe and 200 -240 gll of HCl as described above. However, it is considered that the energy cost of free HCl recovery by reduction of Fe ions in the electrolysis process becomes lower than that by thermal-decomposition process because free HCl exists in the back-extrac-tion solution of the organic solvent (E). As for the ion exchange membrane any ion exchange membrane may be used.
The solution containing Fe2+ ions, which consists of the solution of Fe ions produced by electro-reduction of Fe3+ ions ~FeC13~ FeC12 + Cl) and the solution which is recovered by trans-ferring the solution, containing abundant HCl unused in the back-extraction, into the anode compartment are converted to FeC13 by the oxidation with air or oxygen and one part of Fe ions is pre-cipitated and separated as hydrated Fe oxide or hydroxide accord-ing to the following formula.
, :.
1~7948B
2 FeC12 + O + ~I20 = FeC13 + HCl ~ FeO(O~I) Both HCl and FeC13 produced in the above formula are introduce~ again into the cathode compartment of electrolysis process and HCl and Cl which are transferred to the anode com-partment are recovered by reduction of Fe3+ ions to Fe2+ ions, When there is the apparatus of thermal-decomposition, Fe203 and HCl can be obtained by thermal-decomposition of the concentrated solution produced through several electrolysis processes from view-point of water-balance, Both Fe203 and FeO(OH) obtained as mentioned above are high purity and can be utilized for ferrite and pigment without further purification, The production of TiO2 based on this invention has the following advantages, ~1) The adoption of this production method has the extreme advantages in the anti-pollution and economical cost by working out the problem of FeS04'nH20 - treatment which has been the most troublesome one, (2) The recovery of valuable metals such as V, Nb and Mn, etc, contained in a small amount is possible by regenerating and reusing economically the waste acid, including a large amount of heavy metal ions in 20 - 400/O H2S04 after hydrolysis process, The product of individual valuable metal recovered is high purity, (3) The metals such as Cr which their existence in raw mate-rials is disliked can be fractionally recovered with solvent ex-traction technique from the aqueous solution before hydrolysis pro-cess and consequently the selection of raw materials is very easy, (4) The product-purity of hydrated Fe oxide and hydroxide by-produced in acid recovery process is very high as used for not only pig iron - raw materials but also valuable ferrite or pigment and consequently the economical value is enhanced, (5) The whole system is built up as the closed-circuit and .~
the protection of environment is possible because the great part of used reagent is recovered or used as a product, ' . , .
.
.
.. ~
' ~
. ~ Material of diaphragm : Film of Tetra-~e ethylene Thickness of " : 0.103 mm Void percent " : 55%
Hole diameter " : 0.3~
Water permeability " : 0,48 ml/cm H
Electric resistance : 0.1~ -cm Anod`e : carbon Cathode : Ti (Pt plating) Volume of anode or cathode room : 5 1 Temperature : 24 - 55C
Current densi~y : 2 A/dm - Continuous test at s-teady state -Cathode roorn Anode room Inlet Outlet InletOutlet Fe3 (g/l) 18.0 0.4 0 F 2+ ( " ) 21.0 0 HCl ~ " ) 176 27.4 50 178.0 vqolume(llH) . 5.7 The following diaphragms besides the above one were10 used, Electric Hole Void Water permeability Material resistance dia. %
Acetic 0.05-0.19~2-cm 0.1-0.4~ 58-62%0,11-0,3 ml/cm H
cellose Polypropy- 0,12-0,27 " 0.2-0.4~ 38-45% 0.02-0.2 "
lene Ion exchange 1.7 -3.2 " Water content : 38% , membrane The back-extraction solution of the organic solvent ~E) is the concentrated solution containing 75 - 85 g/l of Fe and 200 -240 gll of HCl as described above. However, it is considered that the energy cost of free HCl recovery by reduction of Fe ions in the electrolysis process becomes lower than that by thermal-decomposition process because free HCl exists in the back-extrac-tion solution of the organic solvent (E). As for the ion exchange membrane any ion exchange membrane may be used.
The solution containing Fe2+ ions, which consists of the solution of Fe ions produced by electro-reduction of Fe3+ ions ~FeC13~ FeC12 + Cl) and the solution which is recovered by trans-ferring the solution, containing abundant HCl unused in the back-extraction, into the anode compartment are converted to FeC13 by the oxidation with air or oxygen and one part of Fe ions is pre-cipitated and separated as hydrated Fe oxide or hydroxide accord-ing to the following formula.
, :.
1~7948B
2 FeC12 + O + ~I20 = FeC13 + HCl ~ FeO(O~I) Both HCl and FeC13 produced in the above formula are introduce~ again into the cathode compartment of electrolysis process and HCl and Cl which are transferred to the anode com-partment are recovered by reduction of Fe3+ ions to Fe2+ ions, When there is the apparatus of thermal-decomposition, Fe203 and HCl can be obtained by thermal-decomposition of the concentrated solution produced through several electrolysis processes from view-point of water-balance, Both Fe203 and FeO(OH) obtained as mentioned above are high purity and can be utilized for ferrite and pigment without further purification, The production of TiO2 based on this invention has the following advantages, ~1) The adoption of this production method has the extreme advantages in the anti-pollution and economical cost by working out the problem of FeS04'nH20 - treatment which has been the most troublesome one, (2) The recovery of valuable metals such as V, Nb and Mn, etc, contained in a small amount is possible by regenerating and reusing economically the waste acid, including a large amount of heavy metal ions in 20 - 400/O H2S04 after hydrolysis process, The product of individual valuable metal recovered is high purity, (3) The metals such as Cr which their existence in raw mate-rials is disliked can be fractionally recovered with solvent ex-traction technique from the aqueous solution before hydrolysis pro-cess and consequently the selection of raw materials is very easy, (4) The product-purity of hydrated Fe oxide and hydroxide by-produced in acid recovery process is very high as used for not only pig iron - raw materials but also valuable ferrite or pigment and consequently the economical value is enhanced, (5) The whole system is built up as the closed-circuit and .~
the protection of environment is possible because the great part of used reagent is recovered or used as a product, ' . , .
.
.
.. ~
' ~
Claims (14)
1. A process for the preparation of titanium dioxide by dissolving titanium-containing raw materials in sulphuric acid to form an aqueous solution of sulphuric acid containing dissolved titanium and other metals, separating ferrous sulphate from the aqueous solution and then isolating titanium as the desired titanium dioxide by the steps of:
a) where dissolved chromium and niobium are present in the aqueous solution, contacting the aqueous solution with an organic extractant (A) capable of extracting chromium and niobium so as to extract the dissolved chromium and niobium from the aqueous solution;
b) hydrolysing the aqueous solution so as to precipitate the majority of dissolved titanium therefrom and subsequently recovering the precipitated titanium compound as titanium dioxide;
c) contacting the hydrolysed aqueous solution with an organic extractant (B) capable of extracting titanium from the aqueous solution for subsequent recovery as titanium dioxide;
d) oxidizing the thus-contacted aqueous solution to convert ferrous ions present therein to ferric ions and contacting the oxidized aqueous solution with an organic extractant (C) capable of extracting ferric ions so as to extract ferric ions from the aqueous solution; and where dissolved vanadium is present in the aqueous solution;
e) contacting the resultant aqueous solution with an organic extractant (D) capable of extracting vanadium so as to extract dissolved vanadium from the aqueous solution to yield a liquor essentially comprising sulphuric acid subs-tantially free from dissolved chromium, niobium, titanium, iron and vanadium.
a) where dissolved chromium and niobium are present in the aqueous solution, contacting the aqueous solution with an organic extractant (A) capable of extracting chromium and niobium so as to extract the dissolved chromium and niobium from the aqueous solution;
b) hydrolysing the aqueous solution so as to precipitate the majority of dissolved titanium therefrom and subsequently recovering the precipitated titanium compound as titanium dioxide;
c) contacting the hydrolysed aqueous solution with an organic extractant (B) capable of extracting titanium from the aqueous solution for subsequent recovery as titanium dioxide;
d) oxidizing the thus-contacted aqueous solution to convert ferrous ions present therein to ferric ions and contacting the oxidized aqueous solution with an organic extractant (C) capable of extracting ferric ions so as to extract ferric ions from the aqueous solution; and where dissolved vanadium is present in the aqueous solution;
e) contacting the resultant aqueous solution with an organic extractant (D) capable of extracting vanadium so as to extract dissolved vanadium from the aqueous solution to yield a liquor essentially comprising sulphuric acid subs-tantially free from dissolved chromium, niobium, titanium, iron and vanadium.
2. A process according to claim 1, which comprises dissolving the raw materials in the aqueous solution which remains after extracting titanium and Fe3+ ions.
3. A process according to claim 1, wherein organic extractant A comprises a primary, secondary, tertiary or quaternary amine.
4. A process according to claim 1, wherein organic extractant B comprises an alkyl phosphoric acid.
5. A process according to claim 1, wherein organic extractant C comprises an alkyl phosphoric acid.
6. A process according to claim 1, wherein organic extractant D comprises a primary, secondary, or tertiary amine.
7. A process according to claim 1, in which the organic extractant B into which Fe is extracted together with Ti is scrubbed with an aqueous solution of H2SO4, HNO3 or HCl and then back-extracted with an aqueous solution of (NH4)2CO3, (NH4)2SO4, NH4F, NH4NO3 alone or combination with NH3 to strip and separate Ti as Ti(OH)4.
8. A method according to claim 1, in which HCl is added to the aqueous solution after the conversion of Fe2+
ions to Fe3+ ions, and the aqueous solution is brought into contact with organic extractant E comprising esters of phos-phates, primary amines, secondary amines, tertiary amines and quaternary amines, diluted with a petroleum hydrocarbon to extract Fe3- ions as an iron chloride complex.
ions to Fe3+ ions, and the aqueous solution is brought into contact with organic extractant E comprising esters of phos-phates, primary amines, secondary amines, tertiary amines and quaternary amines, diluted with a petroleum hydrocarbon to extract Fe3- ions as an iron chloride complex.
9. A method according to claim 7, in which the organic extractant B is scrubbed with HCl, and the resultant aqueous solution containing Fe3+ is brought into contact with the organic solvent E to extract Fe3+ ions as an iron chloride complex.
10. A method according to claim 1, in which the precipi-tate of FeSO4n.H2O is dissolved in water and brought into con-tact with an organic extractant F comprising alkyl phosphoric acids diluted with a petroleum hydrocarbon to extract Mn ions.
11. A method according to claim 10, in which the organic extractant F is brought into contact with a solution of MnSO4 to scrub Fe2+ ions from the solvent to recover a high-purity manganese.
12. A method according to claim 3, in which the organic extractant A is brought into contact with a solution of H2SO4 or HCl to scrub Cr ions and to leave only Nb in the organic solvent.
13. A method according to claim 1, in which the raw material is illumenite.
14. A method according to claim 1, in which the raw material is a metallurgical slag containing titanium.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50055048A JPS51142498A (en) | 1975-05-06 | 1975-05-06 | The production of titanium oxide by sulfuric acid method without the f ormation of ferric sulfate and waste acids. |
| JP50089433A JPS585989B2 (en) | 1975-07-21 | 1975-07-21 | Yukiyo Bio-Site FE |
| JP14486175A JPS5268099A (en) | 1975-12-04 | 1975-12-04 | Recovery process for waste sulfuric acid |
| JP392976A JPS5287000A (en) | 1976-01-16 | 1976-01-16 | Process for preparing titanium oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079488A true CA1079488A (en) | 1980-06-17 |
Family
ID=27453973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA251,611A Expired CA1079488A (en) | 1975-05-06 | 1976-04-30 | Treatment method of raw materials containing titanium |
Country Status (9)
| Country | Link |
|---|---|
| AU (1) | AU505093B2 (en) |
| CA (1) | CA1079488A (en) |
| DE (1) | DE2620065A1 (en) |
| ES (1) | ES447652A1 (en) |
| FI (1) | FI761256A (en) |
| FR (1) | FR2310314A1 (en) |
| GB (1) | GB1552918A (en) |
| IT (1) | IT1071494B (en) |
| NO (1) | NO761531L (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH610935A5 (en) * | 1976-09-03 | 1979-05-15 | Battelle Memorial Institute | Electrochemical reactor intended to be incorporated into a plant for the production of titanium dioxide from ilmenite by the sulphate process |
| US4230542A (en) * | 1978-10-13 | 1980-10-28 | Oronzio De Nora Impianti Elettrochimici S.P.A. | Electrolytic process for treating ilmenite leach solution |
| DE3524053A1 (en) * | 1985-07-05 | 1987-01-08 | Bayer Antwerpen Nv | METHOD FOR PRODUCING HIGH QUALITY TITANIUM DIOXIDE BY THE SULFATE METHOD |
| WO2012126092A1 (en) | 2011-03-18 | 2012-09-27 | Orbite Aluminae Inc. | Processes for recovering rare earth elements from aluminum-bearing materials |
| EP2705169A4 (en) | 2011-05-04 | 2015-04-15 | Orbite Aluminae Inc | Processes for recovering rare earth elements from various ores |
| CN103842296B (en) | 2011-06-03 | 2016-08-24 | 奥贝特科技有限公司 | For the method preparing bloodstone |
| AU2012308068B2 (en) | 2011-09-16 | 2015-02-05 | Orbite Aluminae Inc. | Processes for preparing alumina and various other products |
| US9023301B2 (en) | 2012-01-10 | 2015-05-05 | Orbite Aluminae Inc. | Processes for treating red mud |
| WO2013142957A1 (en) | 2012-03-29 | 2013-10-03 | Orbite Aluminae Inc. | Processes for treating fly ashes |
| BR112015000626A2 (en) | 2012-07-12 | 2017-06-27 | Orbite Aluminae Inc | processes for preparing titanium oxide and other miscellaneous products |
| CA2885255C (en) | 2012-09-26 | 2015-12-22 | Orbite Aluminae Inc. | Processes for preparing alumina and magnesium chloride by hc1 leaching of various materials |
| EP2920114A4 (en) | 2012-11-14 | 2016-03-02 | Orbite Aluminae Inc | Methods for purifying aluminium ions |
| CN107364899B (en) * | 2017-07-21 | 2019-04-05 | 湖南众鑫新材料科技股份有限公司 | A method of alum iron is produced using smelted furnace cinder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3067010A (en) * | 1960-10-19 | 1962-12-04 | Dow Chemical Co | Process for preparation of titanium dioxide |
| FR1322201A (en) * | 1962-02-02 | 1963-03-29 | Dow Chemical Co | Process for the preparation of high purity titanium dioxide and product thus obtained |
-
1976
- 1976-04-30 CA CA251,611A patent/CA1079488A/en not_active Expired
- 1976-05-04 NO NO761531A patent/NO761531L/no unknown
- 1976-05-04 IT IT22942/76A patent/IT1071494B/en active
- 1976-05-05 AU AU13637/76A patent/AU505093B2/en not_active Expired
- 1976-05-05 FR FR7613438A patent/FR2310314A1/en active Granted
- 1976-05-05 FI FI761256A patent/FI761256A/fi not_active Application Discontinuation
- 1976-05-06 ES ES447652A patent/ES447652A1/en not_active Expired
- 1976-05-06 GB GB18701/76A patent/GB1552918A/en not_active Expired
- 1976-05-06 DE DE19762620065 patent/DE2620065A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| GB1552918A (en) | 1979-09-19 |
| FR2310314A1 (en) | 1976-12-03 |
| DE2620065A1 (en) | 1976-11-25 |
| ES447652A1 (en) | 1977-10-01 |
| AU1363776A (en) | 1977-11-10 |
| FR2310314B1 (en) | 1981-04-17 |
| NO761531L (en) | 1976-11-09 |
| IT1071494B (en) | 1985-04-10 |
| AU505093B2 (en) | 1979-11-08 |
| FI761256A (en) | 1976-11-07 |
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