CA3018028A1 - Recovery of metals from calcium-rich materials - Google Patents
Recovery of metals from calcium-rich materials Download PDFInfo
- Publication number
- CA3018028A1 CA3018028A1 CA3018028A CA3018028A CA3018028A1 CA 3018028 A1 CA3018028 A1 CA 3018028A1 CA 3018028 A CA3018028 A CA 3018028A CA 3018028 A CA3018028 A CA 3018028A CA 3018028 A1 CA3018028 A1 CA 3018028A1
- Authority
- CA
- Canada
- Prior art keywords
- calcium
- slag
- containing material
- rich
- iron
- 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.)
- Granted
Links
- 239000011575 calcium Substances 0.000 title claims abstract description 217
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 203
- 239000000463 material Substances 0.000 title claims abstract description 130
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 150000002739 metals Chemical class 0.000 title description 13
- 238000011084 recovery Methods 0.000 title description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 192
- 229910052742 iron Inorganic materials 0.000 claims abstract description 96
- 238000002386 leaching Methods 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 69
- 230000008569 process Effects 0.000 claims abstract description 69
- 229960005069 calcium Drugs 0.000 claims description 196
- 235000001465 calcium Nutrition 0.000 claims description 196
- 239000002893 slag Substances 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 43
- 229910052720 vanadium Inorganic materials 0.000 claims description 38
- 238000003723 Smelting Methods 0.000 claims description 33
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 235000010216 calcium carbonate Nutrition 0.000 claims description 6
- 229960003563 calcium carbonate Drugs 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 description 24
- 235000002639 sodium chloride Nutrition 0.000 description 17
- 239000003638 chemical reducing agent Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 229910052609 olivine Inorganic materials 0.000 description 4
- 239000010450 olivine Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- -1 iron silicates Chemical class 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWWOZCUXMGDXEX-UHFFFAOYSA-N [Fe+2].[O-2].[V+5] Chemical class [Fe+2].[O-2].[V+5] DWWOZCUXMGDXEX-UHFFFAOYSA-N 0.000 description 1
- GJPIVNTZJFSDCX-UHFFFAOYSA-N [V].[Ca] Chemical compound [V].[Ca] GJPIVNTZJFSDCX-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001719 melilite Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001720 Åkermanite 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- 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
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Provided herein is a process for recovering metal(s) from calcium rich iron containing material (8), comprising (a) leaching (1) calcium one or more times from said calcium rich iron containing material (8) to obtain a calcium depleted iron containing material (13); and (b) subjecting the calcium depleted iron containing material (13) to pyrometallurgical treatment (3) to recover metal(s) (17) from said calcium depleted iron containing material (13).
Description
RECOVERY OF METALS FROM CALCIUM-RICH MATERIALS
FIELD OF THE INVENTION
The present invention relates to recovery of valuable metals from cal-cium rich iron containing materials by pyrometallurgical treatment and more par-s ticularly to process comprising removal of calcium from the calcium rich iron con-taining starting material prior to the pyrometallurgical treatment.
BACKGROUND OF THE INVENTION
Some steel plants use iron ore that contains vanadium and other resi-due metals. These metals and other nonferrous oxides typically end up in the slag in during the steelmaking process. This slag is typically landfilled and not used as a product due to the fact that it contains the said metal oxide residues that have been proved to be harmful for the environment. The conventional way to recover these valuable metals is to subject the said slag to smelting.
During the smelting process most of the iron- and vanadium oxides 15 (along with other trace alloying metals) are reduced to the metal phase in the presence of a reductant (typically carbon bearing anthracite, coke or metallic re-ductants, typically Al, FeSi or any other reducing substance). Typically the smelt-ing vessel is an electric arc furnace (alternating current or direct current type).
During the smelting process other unreduced oxides form the furnace slag, Calci-20 um oxide in this slag makes the liquidus temperature of the slag high and as much as 24% w/w silica flux of total solid feed to the furnace may be required for melt-ing the slag. This amount reflects a situation where the fluxing mix consists solely of quartz and calcium content of the feed material is 45% w/w calculated as CaO.
One of the disadvantages associated with the use of flux material is 25 that impurities resulting from the flux material end up in the obtained products.
In this case metal product silicon content will be higher when silica flux is used.
This is due to the higher silicon oxide input into the furnace compared to the amount of formed metal, which stays roughly at the same level regardless of the used flux amount. Typically some percentage of the silicon fed to the system re-30 ports to the metal phase. Therefore when tonnage of input silicon is higher while rest of metal forming components stay the same, the metal silicon content will be higher also.
FIELD OF THE INVENTION
The present invention relates to recovery of valuable metals from cal-cium rich iron containing materials by pyrometallurgical treatment and more par-s ticularly to process comprising removal of calcium from the calcium rich iron con-taining starting material prior to the pyrometallurgical treatment.
BACKGROUND OF THE INVENTION
Some steel plants use iron ore that contains vanadium and other resi-due metals. These metals and other nonferrous oxides typically end up in the slag in during the steelmaking process. This slag is typically landfilled and not used as a product due to the fact that it contains the said metal oxide residues that have been proved to be harmful for the environment. The conventional way to recover these valuable metals is to subject the said slag to smelting.
During the smelting process most of the iron- and vanadium oxides 15 (along with other trace alloying metals) are reduced to the metal phase in the presence of a reductant (typically carbon bearing anthracite, coke or metallic re-ductants, typically Al, FeSi or any other reducing substance). Typically the smelt-ing vessel is an electric arc furnace (alternating current or direct current type).
During the smelting process other unreduced oxides form the furnace slag, Calci-20 um oxide in this slag makes the liquidus temperature of the slag high and as much as 24% w/w silica flux of total solid feed to the furnace may be required for melt-ing the slag. This amount reflects a situation where the fluxing mix consists solely of quartz and calcium content of the feed material is 45% w/w calculated as CaO.
One of the disadvantages associated with the use of flux material is 25 that impurities resulting from the flux material end up in the obtained products.
In this case metal product silicon content will be higher when silica flux is used.
This is due to the higher silicon oxide input into the furnace compared to the amount of formed metal, which stays roughly at the same level regardless of the used flux amount. Typically some percentage of the silicon fed to the system re-30 ports to the metal phase. Therefore when tonnage of input silicon is higher while rest of metal forming components stay the same, the metal silicon content will be higher also.
2 The metal phase from the smelting goes to a converting step, where vanadium and other valuable metals are selectively oxidized to the slag. The slag is further treated with salt roasting. In the salt roasting calcium further forms in-soluble salts, in particular with vanadium, which causes losses in the following hydrometallurgical treatment stages if calcium is not removed to the sufficient level in the previous processing steps.
BRIEF DESCRIPTION OF THE INVENTION
An object of the present invention is thus to provide a process for re-covery of valuable metal(s) from calcium rich iron containing materials so as to overcome the above problems. The objects of the invention are achieved by pro-cesses which are characterized by what is stated in the independent claims.
The preferred embodiments of the invention are disclosed in the dependent claims.
The invention is based on the surprizing realization that removal of calcium from calcium rich iron containing starting material prior to pyrometal-lurgical treatment by leaching allows more efficient pyrometallurgical treatment.
Removal of calcium from the material lowers the liquidus temperature of the ma-terial in smelting and thus lowers the required amount of flux material or even makes use of flux material redundant. As a result the smelting phase feed amount, residual slag amount and energy consumption are significantly lower. Removal of calcium may also improve the quality of the products obtained from the pyromet-allurgical treatment.
This invention can also be utilized to a processing option of feeding the starting material after removal of calcium straight to roasting without the previ-ously explained smelting and converting steps. It is possible to reach such a low levels of calcium after the removal of calcium to avoid excessive formation of in-soluble calcium salts in the roasting.
Another benefit of the present process is that calcium removal step removes hydroxides and carbonates bound in calcium such as Ca(OH)2 and CaCO3.
This lowers furnace energy and reductant consumption and makes gas handling and pressure control of the furnace easier and therefore safer. In the conventional smelting process if the slag is stored outside pre-drying under 200 C only re-moves free water and some of crystal waters and all hydroxides and carbonates are left to the furnace feed.
BRIEF DESCRIPTION OF THE INVENTION
An object of the present invention is thus to provide a process for re-covery of valuable metal(s) from calcium rich iron containing materials so as to overcome the above problems. The objects of the invention are achieved by pro-cesses which are characterized by what is stated in the independent claims.
The preferred embodiments of the invention are disclosed in the dependent claims.
The invention is based on the surprizing realization that removal of calcium from calcium rich iron containing starting material prior to pyrometal-lurgical treatment by leaching allows more efficient pyrometallurgical treatment.
Removal of calcium from the material lowers the liquidus temperature of the ma-terial in smelting and thus lowers the required amount of flux material or even makes use of flux material redundant. As a result the smelting phase feed amount, residual slag amount and energy consumption are significantly lower. Removal of calcium may also improve the quality of the products obtained from the pyromet-allurgical treatment.
This invention can also be utilized to a processing option of feeding the starting material after removal of calcium straight to roasting without the previ-ously explained smelting and converting steps. It is possible to reach such a low levels of calcium after the removal of calcium to avoid excessive formation of in-soluble calcium salts in the roasting.
Another benefit of the present process is that calcium removal step removes hydroxides and carbonates bound in calcium such as Ca(OH)2 and CaCO3.
This lowers furnace energy and reductant consumption and makes gas handling and pressure control of the furnace easier and therefore safer. In the conventional smelting process if the slag is stored outside pre-drying under 200 C only re-moves free water and some of crystal waters and all hydroxides and carbonates are left to the furnace feed.
3 BRIEF DESCRIPTION OF THE DRAWINGS
In the following the invention will be described in greater detail by means of preferred embodiments with reference to the attached drawings, in which Figure 1 shows a first example of the present process;
Figure 2 shows a second example of the present process;
Figure 3 shows a third example of the present process; and Figure 4 shows a fourth example of the present process.
DETAILED DESCRIPTION OF THE INVENTION
Provided herein is a process for recovery of metal(s) from a calcium rich iron containing material, comprising (a) leaching calcium one or more times from said calcium rich iron containing material to obtain a calcium depleted iron containing material; and (b) subjecting the calcium depleted iron containing material to pyro-metallurgical treatment to recover metal(s) from said calcium depleted iron con-taining material.
The term "calcium rich iron containing material" refers to materials comprising calcium, iron and optionally other valuable metal(s). Said other valu-able metals are typically at least vanadium. Typically the calcium rich iron con-taming material comprises at least 20% w/w, in particular at least 25% w/w, more particularly at least 30% w/w, even more particularly at least 40% w/w, calcium. Calcium is typically present as CaO, Ca(OH)2, CaCO3, calcium silicates and/or other calcium containing compounds. Typically the calcium rich iron con-taining material comprises at least 5% w/w, in particular at least 10% w/w, more particularly at least 15% w/w, iron. In particular the calcium rich iron containing material comprises from 5 to 60% w/w iron. Iron is typically present as Fe304, Fe2O3, FeO, metallic Fe and/or iron silicates.
In particular the calcium rich iron containing material further com-prises vanadium, typically at least 0.2% w/w, in particular at least 0.5% w/w, more particular at least 1% w/w, even more particularly at least 1.5% w/w. Va-nadium is typically present as vanadium oxide(s), in particular V205.
A typical example of a calcium rich iron containing material suitable to be treated by the present process is slag, such as steel converter slag or steel mak-ing slag. A particular example of said calcium rich iron containing material is LD
slag, also known as basic oxygen furnace slag (BOS) or LD-converter slag, a by-
In the following the invention will be described in greater detail by means of preferred embodiments with reference to the attached drawings, in which Figure 1 shows a first example of the present process;
Figure 2 shows a second example of the present process;
Figure 3 shows a third example of the present process; and Figure 4 shows a fourth example of the present process.
DETAILED DESCRIPTION OF THE INVENTION
Provided herein is a process for recovery of metal(s) from a calcium rich iron containing material, comprising (a) leaching calcium one or more times from said calcium rich iron containing material to obtain a calcium depleted iron containing material; and (b) subjecting the calcium depleted iron containing material to pyro-metallurgical treatment to recover metal(s) from said calcium depleted iron con-taining material.
The term "calcium rich iron containing material" refers to materials comprising calcium, iron and optionally other valuable metal(s). Said other valu-able metals are typically at least vanadium. Typically the calcium rich iron con-taming material comprises at least 20% w/w, in particular at least 25% w/w, more particularly at least 30% w/w, even more particularly at least 40% w/w, calcium. Calcium is typically present as CaO, Ca(OH)2, CaCO3, calcium silicates and/or other calcium containing compounds. Typically the calcium rich iron con-taining material comprises at least 5% w/w, in particular at least 10% w/w, more particularly at least 15% w/w, iron. In particular the calcium rich iron containing material comprises from 5 to 60% w/w iron. Iron is typically present as Fe304, Fe2O3, FeO, metallic Fe and/or iron silicates.
In particular the calcium rich iron containing material further com-prises vanadium, typically at least 0.2% w/w, in particular at least 0.5% w/w, more particular at least 1% w/w, even more particularly at least 1.5% w/w. Va-nadium is typically present as vanadium oxide(s), in particular V205.
A typical example of a calcium rich iron containing material suitable to be treated by the present process is slag, such as steel converter slag or steel mak-ing slag. A particular example of said calcium rich iron containing material is LD
slag, also known as basic oxygen furnace slag (BOS) or LD-converter slag, a by-
4 product of the Linz-Donawitz process where pig iron is processed into crude steel.
A particular example of the present process is a process for recovering iron and vanadium from LD slag, comprising (o) providing LD slag;
(i) leaching calcium one or more times from said LD slag to obtain cal-cium depleted LD slag; and (ii) subjecting the calcium depleted LD slag to pyrometallurgical treatment to recover iron and vanadium from the calcium depleted LD slag.
The term "comprise" as used herein and hereafter describes the re-ferred items in a non-limiting manner, e.g. the present processes comprising de-fined process stages consist, at least, of the said stages, but may additionally, when desired, comprise other process stages. However, the processes comprising defined process stages may consist of only the said process stages.
In accordance with the present process the present calcium rich iron containing material is subjected to (a) leaching to remove calcium from the mate-rial prior to (b) pyrometallurgical treatment(s).
Figure 1 shows a first example of the present process wherein calcium rich iron containing material 8 is fed to a calcium removal stage 1, wherein the calcium removal is accomplished by leaching in a (calcium poor) leaching solution 10 to obtain a calcium depleted material 13 and calcium rich leaching solution 9.
The thus obtained calcium depleted iron containing material 13 is then fed to a pyrometallurgical treatment stage, which in this example is a smelting stage 3 performed under an elevated temperature and reducing conditions and in the presence of a flux material 14 to obtain hot metal 17 which comprises the desired valuable metals, slag 15 and evaporated material 16. The calcium rich leaching solution 9 obtained from the calcium removal stage 1 is subjected to calcium pre-cipitation 2 by feeding a carbon dioxide containing gas 11 into the calcium rich leaching solution to precipitate calcium carbonate (CaCO3) 12 and to obtain a cal-cium poor leaching solution 10 which is then recirculated back to the calcium re-moval stage 1.
Figure 2 shows a second example of the present process. In the pro-cess illustrated in Figure 2 a calcium rich iron containing material 8 is subjected to a calcium removal stage 1 accomplished by leaching in a (calcium poor) leach-ing solution 10 to obtain a calcium depleted iron containing material 13 and cal-cium rich leaching solution 9. The thus obtained calcium depleted iron containing material 13 is then fed to a pyrometallurgical treatment stage, which in this ex-ample is a roasting stage 5 performed under an elevated temperature, typically in the presence of salt(s), to obtain a roasted slag 20 which comprises the desired valuable metals. Calcium rich leaching solution 9 obtained from the calcium re-
A particular example of the present process is a process for recovering iron and vanadium from LD slag, comprising (o) providing LD slag;
(i) leaching calcium one or more times from said LD slag to obtain cal-cium depleted LD slag; and (ii) subjecting the calcium depleted LD slag to pyrometallurgical treatment to recover iron and vanadium from the calcium depleted LD slag.
The term "comprise" as used herein and hereafter describes the re-ferred items in a non-limiting manner, e.g. the present processes comprising de-fined process stages consist, at least, of the said stages, but may additionally, when desired, comprise other process stages. However, the processes comprising defined process stages may consist of only the said process stages.
In accordance with the present process the present calcium rich iron containing material is subjected to (a) leaching to remove calcium from the mate-rial prior to (b) pyrometallurgical treatment(s).
Figure 1 shows a first example of the present process wherein calcium rich iron containing material 8 is fed to a calcium removal stage 1, wherein the calcium removal is accomplished by leaching in a (calcium poor) leaching solution 10 to obtain a calcium depleted material 13 and calcium rich leaching solution 9.
The thus obtained calcium depleted iron containing material 13 is then fed to a pyrometallurgical treatment stage, which in this example is a smelting stage 3 performed under an elevated temperature and reducing conditions and in the presence of a flux material 14 to obtain hot metal 17 which comprises the desired valuable metals, slag 15 and evaporated material 16. The calcium rich leaching solution 9 obtained from the calcium removal stage 1 is subjected to calcium pre-cipitation 2 by feeding a carbon dioxide containing gas 11 into the calcium rich leaching solution to precipitate calcium carbonate (CaCO3) 12 and to obtain a cal-cium poor leaching solution 10 which is then recirculated back to the calcium re-moval stage 1.
Figure 2 shows a second example of the present process. In the pro-cess illustrated in Figure 2 a calcium rich iron containing material 8 is subjected to a calcium removal stage 1 accomplished by leaching in a (calcium poor) leach-ing solution 10 to obtain a calcium depleted iron containing material 13 and cal-cium rich leaching solution 9. The thus obtained calcium depleted iron containing material 13 is then fed to a pyrometallurgical treatment stage, which in this ex-ample is a roasting stage 5 performed under an elevated temperature, typically in the presence of salt(s), to obtain a roasted slag 20 which comprises the desired valuable metals. Calcium rich leaching solution 9 obtained from the calcium re-
5 moval stage 1 is subjected to calcium precipitation 2 by feeding a carbon dioxide containing gas 11 into the calcium rich leaching solution to obtain calcium car-bonate (CaCO3) 12 and a calcium poor leaching solution 10 which is recirculated to the calcium removal stage 1.
Suitable leaching solutions for removing calcium from the calcium rich iron containing material in stage (a), and similarly in stage (i), are e.g.
those se-lected from the group consisting of acetic acid, nitric acid, propionic acid, aqueous solutions of ammonium salts, such as aqueous solution of ammonium acetate (CH3COONH4), ammonium chloride (NH4CI) or ammonium nitrate (NH4NO3), Preferably the present leaching solution is an aqueous salt solution, in particular an aqueous solution of an ammonium salt, more particularly an aqueous solution of ammonium acetate (CH3COONH4), ammonium chloride (NH4CI) or ammonium nitrate (NH4NO3), most preferably ammonium chloride (NH4C1). The salt concen-tration of the aqueous salt solution is typically from 0.2 to 8 M, preferably 0.5 to 5 M, more preferably 0.5 to 2 M.
Leaching in the calcium removal stage (a), and similarly in stage (i), is typically performed at a temperature of from 0 to 100 C, preferably from 10 to 70 C, more preferably from 20 to 70 C. Most preferably, the leaching is performed at temperature of 20 to 60 C, using an aqueous salt solution. The desired crystal form of the precipitated calcium carbonate has an effect on the leaching tempera-ture since different crystal forms precipitate in different temperatures and the solution is circulated. There is no need to cool down or heat the solution before leaching stage.
Leaching in the calcium removal stage (a), and similarly in stage (i), may be performed one or more times.
As calcium removal is stage (a), and similarly in stage (i), is performed to lower the calcium concentration in the feed to the pyrometallurgical treatment stage (b), and similarly to stage (ii), and in smelting some calcium is needed to lower the liquidus temperature of the slag, it is a matter of optimization whether the calcium is removed only partly in the calcium removal stage (a), and similarly in stage (i), and/or whether some calcium rich iron containing material is fed di-rectly to the smelting without calcium removal, or whether calcium is removed as
Suitable leaching solutions for removing calcium from the calcium rich iron containing material in stage (a), and similarly in stage (i), are e.g.
those se-lected from the group consisting of acetic acid, nitric acid, propionic acid, aqueous solutions of ammonium salts, such as aqueous solution of ammonium acetate (CH3COONH4), ammonium chloride (NH4CI) or ammonium nitrate (NH4NO3), Preferably the present leaching solution is an aqueous salt solution, in particular an aqueous solution of an ammonium salt, more particularly an aqueous solution of ammonium acetate (CH3COONH4), ammonium chloride (NH4CI) or ammonium nitrate (NH4NO3), most preferably ammonium chloride (NH4C1). The salt concen-tration of the aqueous salt solution is typically from 0.2 to 8 M, preferably 0.5 to 5 M, more preferably 0.5 to 2 M.
Leaching in the calcium removal stage (a), and similarly in stage (i), is typically performed at a temperature of from 0 to 100 C, preferably from 10 to 70 C, more preferably from 20 to 70 C. Most preferably, the leaching is performed at temperature of 20 to 60 C, using an aqueous salt solution. The desired crystal form of the precipitated calcium carbonate has an effect on the leaching tempera-ture since different crystal forms precipitate in different temperatures and the solution is circulated. There is no need to cool down or heat the solution before leaching stage.
Leaching in the calcium removal stage (a), and similarly in stage (i), may be performed one or more times.
As calcium removal is stage (a), and similarly in stage (i), is performed to lower the calcium concentration in the feed to the pyrometallurgical treatment stage (b), and similarly to stage (ii), and in smelting some calcium is needed to lower the liquidus temperature of the slag, it is a matter of optimization whether the calcium is removed only partly in the calcium removal stage (a), and similarly in stage (i), and/or whether some calcium rich iron containing material is fed di-rectly to the smelting without calcium removal, or whether calcium is removed as
6 much as possible in the calcium removal stage (a), and similarly in stage (i).
Pref-erably at least 60% w/w of the calcium present in the calcium rich iron containing material is removed.
When calcium is desired to be removed only partly, it is preferred to perform a single stage leaching in stage (a), and similarly in stage (i), and prefera-bly to remove from 60 to 90% w/w, more preferably from 65 to 85% w/w of the calcium from the calcium rich iron containing material. In this case the amount of calcium in the calcium depleted iron containing material is preferably below 25%
w/w, more preferably below 20% w/w, even more preferably below 17% w/w.
When as much calcium as possible is desired to be removed, then leaching is preferably repeated until at least 70% w/w, more preferably from 75% to 100% w/w, even more preferably from 80% to 99% of the calcium pre-sent in the calcium rich iron containing material is removed. In this case the amount of calcium in the calcium depleted iron containing material is preferably below 20% w/w, more preferably below 15% w/w, even more preferably below 10% w/w, most preferably below 1% w/w. Typically when calcium is needed to be removed as much as possible, the calcium leaching stage (a) or (i) is performed twice. The number of leaching stages indicated herein refers to number of times of taking a fresh (calcium poor) leaching solution to the leaching stage (a), and similarly to stage (i). Accordingly the several leaching stages may also be per-formed as separate leaching stages wherein leaching is performed in consecutive-ly arranged leaching vessels or in a single leaching vessel which is successively refilled with fresh (calcium poor) leaching solution.
As discussed above in context of the first and second examples, in step (a), and similarly in step (i), in addition to the calcium depleted iron containing material, a used leaching solution containing calcium dissolved from the calcium rich iron containing material is obtained. Herein and hereafter said used leaching solution is also referred to as a calcium rich leaching solution. If recovery and re-use of said used leaching solution is desired, calcium should be removed from the used leaching solution to obtain a calcium poor leaching solution. Preferably this is accomplished by precipitation.
A typical example of precipitation of the calcium from the calcium rich leaching solution is carbonation. This may be accomplished by (c) optionally first filtering the used calcium rich leaching solution to remove any residual calcium rich iron containing material from said calcium rich leaching solution; and (d) bubbling carbon dioxide containing gas, in particular carbon dioxide, into the cal-
Pref-erably at least 60% w/w of the calcium present in the calcium rich iron containing material is removed.
When calcium is desired to be removed only partly, it is preferred to perform a single stage leaching in stage (a), and similarly in stage (i), and prefera-bly to remove from 60 to 90% w/w, more preferably from 65 to 85% w/w of the calcium from the calcium rich iron containing material. In this case the amount of calcium in the calcium depleted iron containing material is preferably below 25%
w/w, more preferably below 20% w/w, even more preferably below 17% w/w.
When as much calcium as possible is desired to be removed, then leaching is preferably repeated until at least 70% w/w, more preferably from 75% to 100% w/w, even more preferably from 80% to 99% of the calcium pre-sent in the calcium rich iron containing material is removed. In this case the amount of calcium in the calcium depleted iron containing material is preferably below 20% w/w, more preferably below 15% w/w, even more preferably below 10% w/w, most preferably below 1% w/w. Typically when calcium is needed to be removed as much as possible, the calcium leaching stage (a) or (i) is performed twice. The number of leaching stages indicated herein refers to number of times of taking a fresh (calcium poor) leaching solution to the leaching stage (a), and similarly to stage (i). Accordingly the several leaching stages may also be per-formed as separate leaching stages wherein leaching is performed in consecutive-ly arranged leaching vessels or in a single leaching vessel which is successively refilled with fresh (calcium poor) leaching solution.
As discussed above in context of the first and second examples, in step (a), and similarly in step (i), in addition to the calcium depleted iron containing material, a used leaching solution containing calcium dissolved from the calcium rich iron containing material is obtained. Herein and hereafter said used leaching solution is also referred to as a calcium rich leaching solution. If recovery and re-use of said used leaching solution is desired, calcium should be removed from the used leaching solution to obtain a calcium poor leaching solution. Preferably this is accomplished by precipitation.
A typical example of precipitation of the calcium from the calcium rich leaching solution is carbonation. This may be accomplished by (c) optionally first filtering the used calcium rich leaching solution to remove any residual calcium rich iron containing material from said calcium rich leaching solution; and (d) bubbling carbon dioxide containing gas, in particular carbon dioxide, into the cal-
7 cium rich leaching solution to precipitate calcium carbonate and thus to remove calcium from said calcium rich leaching solution to obtain a regenerated calcium poor leaching solution. Said regenerated calcium poor leaching solution may then be (e) recycled to stage (a) or (i), respectively. The carbon dioxide required in stage (d) may be obtained e.g. from flue gas or other sources. The temperature of the carbonation depends on the desired crystal form of the precipitated calcium carbonate. Different crystal forms precipitate in different temperatures, for ex-ample aragonite can be precipitated at 60 C.
After removal of calcium from the material, the calcium depleted iron containing material is subjected to a pyrometallurgical treatment stage (b) or (ii).
Before feeding the calcium depleted iron containing material to the pyrometallur-gical treatment stage (b) or (ii) said calcium depleted iron containing material is preferably dried.
The present pyrometallurgical treatment stage (b) or (ii) may be any one or more pyrometallurgical treatment(s) known to a skilled person and found suitable for recovering desired valuable metals from the treated calcium depleted iron containing material. Typically the pyrometallurgical treatment is at least smelting or roasting. Preferably the calcium depleted material is subjected to at least smelting.
Due to the previous calcium removal stage (a) or (i) the mass flow of the calcium depleted iron containing material to the pyrometallurgical stage (b) or (ii), respectively, is smaller as compared to untreated calcium rich iron con-taining material as calcium is one of the major elements in the calcium rich iron containing material. This allows reduction of furnace size and decreases the amount of needed electricity during the pyrometallurgical treatment and/or al-lows increase of the capacity.
Further, the liquidus temperature of a mixture of said calcium deplet-ed iron containing material and optional desired amount of untreated calcium rich iron containing material is lower as compared to the respective untreated calcium rich iron containing material. Therefore the use of flux materials is mini-mized. This is relevant in particular when the material is subjected to smelting in stage (b), and similarly in stage (ii).
In cases where reaching of desired slag region requires addition of cal-cium containing material it may be possible to also add some untreated calcium rich iron containing material to the pyrometallurgical process stage.
After removal of calcium from the material, the calcium depleted iron containing material is subjected to a pyrometallurgical treatment stage (b) or (ii).
Before feeding the calcium depleted iron containing material to the pyrometallur-gical treatment stage (b) or (ii) said calcium depleted iron containing material is preferably dried.
The present pyrometallurgical treatment stage (b) or (ii) may be any one or more pyrometallurgical treatment(s) known to a skilled person and found suitable for recovering desired valuable metals from the treated calcium depleted iron containing material. Typically the pyrometallurgical treatment is at least smelting or roasting. Preferably the calcium depleted material is subjected to at least smelting.
Due to the previous calcium removal stage (a) or (i) the mass flow of the calcium depleted iron containing material to the pyrometallurgical stage (b) or (ii), respectively, is smaller as compared to untreated calcium rich iron con-taining material as calcium is one of the major elements in the calcium rich iron containing material. This allows reduction of furnace size and decreases the amount of needed electricity during the pyrometallurgical treatment and/or al-lows increase of the capacity.
Further, the liquidus temperature of a mixture of said calcium deplet-ed iron containing material and optional desired amount of untreated calcium rich iron containing material is lower as compared to the respective untreated calcium rich iron containing material. Therefore the use of flux materials is mini-mized. This is relevant in particular when the material is subjected to smelting in stage (b), and similarly in stage (ii).
In cases where reaching of desired slag region requires addition of cal-cium containing material it may be possible to also add some untreated calcium rich iron containing material to the pyrometallurgical process stage.
8 In accordance with the present process flux material may be used to reach the correct slag region in the smelting stage. Preferably the amount of add-ed flux material (being other than the original calcium rich iron containing feed material without calcium removal treatment) is less than 45% w/w, more prefer-s ably less than 15% w/w and in some cases no fluxes are needed. Possible flux ma-terials include conventional flux materials such as those selected from the group consisting of lime, wollastonite, bauxite, quartz and olivine, as well as other mate-rial comprising SiO2, CaO, MgO, and/or A1203.
Furthermore, iron and/or iron pellets or any other material compris-ing FeO, Fe304, Fe2O3 and/or V205 or other materials containing significant por-tion of iron and/or vanadium may be added when desired. Preferably in smelting the slag region is selected to minimize the fluxing in the smelting. The following slag regions are possible: as merwinite, mellilite, rankinite, akermanite, fosterite, spinel, monticellite, pseudowollastonite, pyroxene, dicalciumsilicate, periclase, anorthite, cordierite, mullite and other similar regions.
When the calcium deplete iron containing material is subjected to smelting in stage (b), and similarly in stage (ii), the smelting stage may be per-formed under conditions known to a skilled person, i.e. under elevated tempera-ture and reducing conditions and in the presence of optional flux material(s) as discussed above. Coke is typically used as a carbon reductant in the smelting stage; however the carbon reductant can be any other carbon bearing reductant, such as anthracite. Reductant may also be metallic reductant, use of which affects energy consumption and feed rates. The smelting may be followed by converting when so desired. The smelting and the optional converting may also be followed by roasting when so desired.
In cases where iron containing material is fed directly to a roasting process without a smelting phase, it may form insoluble vanadium bearing calci-um salts if it comprises excessive amounts of calcium. To minimize the formation of such salts the calcium needs to be removed from the untreated calcium rich iron containing as much as possible in the calcium removal stage (a) or (i).
When the calcium deplete iron containing material is subjected to roasting in stage (b) and similarly in stage (ii), the roasting stage may be performed under conditions known to a skilled person, i.e. under elevated temperature, typically in the pres-ence of salt(s), to obtain a roasted slag. Salts used in the roasting stage are con-ventionally NaCl, Na2CO3 and Na2SO4.
Furthermore, iron and/or iron pellets or any other material compris-ing FeO, Fe304, Fe2O3 and/or V205 or other materials containing significant por-tion of iron and/or vanadium may be added when desired. Preferably in smelting the slag region is selected to minimize the fluxing in the smelting. The following slag regions are possible: as merwinite, mellilite, rankinite, akermanite, fosterite, spinel, monticellite, pseudowollastonite, pyroxene, dicalciumsilicate, periclase, anorthite, cordierite, mullite and other similar regions.
When the calcium deplete iron containing material is subjected to smelting in stage (b), and similarly in stage (ii), the smelting stage may be per-formed under conditions known to a skilled person, i.e. under elevated tempera-ture and reducing conditions and in the presence of optional flux material(s) as discussed above. Coke is typically used as a carbon reductant in the smelting stage; however the carbon reductant can be any other carbon bearing reductant, such as anthracite. Reductant may also be metallic reductant, use of which affects energy consumption and feed rates. The smelting may be followed by converting when so desired. The smelting and the optional converting may also be followed by roasting when so desired.
In cases where iron containing material is fed directly to a roasting process without a smelting phase, it may form insoluble vanadium bearing calci-um salts if it comprises excessive amounts of calcium. To minimize the formation of such salts the calcium needs to be removed from the untreated calcium rich iron containing as much as possible in the calcium removal stage (a) or (i).
When the calcium deplete iron containing material is subjected to roasting in stage (b) and similarly in stage (ii), the roasting stage may be performed under conditions known to a skilled person, i.e. under elevated temperature, typically in the pres-ence of salt(s), to obtain a roasted slag. Salts used in the roasting stage are con-ventionally NaCl, Na2CO3 and Na2SO4.
9 The calcium depleted iron containing material is preferably fed into the pyrometallurgical stage (b) or (ii) as fine material. It may also be pelletized, sintered and/or pre-treated by any other suitable means known to a skilled per-son.
Figure 3 shows a third example of the present process wherein calci-um rich iron containing material further comprising vanadium 8 is subjected to a calcium removal stage 1 accomplished by leaching in a (calcium poor) leaching solution 10. The obtained calcium depleted iron and vanadium containing materi-al 13 is then subjected to a smelting stage 3 under elevated temperature and re-in ducing conditions in the presence of flux material(s) 14 to obtain hot metal 17 which comprises iron and vanadium, slag 15 and evaporated material 16. The calcium rich leaching solution 9 obtained from the calcium removal stage 1 is sub-jected to calcium precipitation 2 by feeding a carbon dioxide containing gas into the calcium rich leaching solution to precipitate calcium carbonate (CaCO3) 12 and to obtain a calcium poor leaching solution 10 which is recirculated to the calcium removal stage 1. Hot metal 17 comprising iron and vanadium obtained from smelting 3 is then subjected to converting 4 to obtain pig iron 18 and slag comprising vanadium and iron 19. The slag 19 is then subjected to roasting 5 per-formed under an elevated temperature, typically in the presence of salt(s), to ob-tam n roasted slag 20 which comprises vanadium and iron and which is then fur-ther subjected to hydrometallurgical treatment 6 to obtain a stream comprising iron and vanadium 22 and rejected material 21. The stream comprising iron and vanadium 22 is then subjected to an aluminothermic reduction treatment 7 to obtain ferrovanadium 23.
Figure 4 shows a fourth example of the present process wherein calci-um rich iron containing material further comprising vanadium 8 is subjected to a calcium removal stage 1 accomplished by leaching in a (calcium poor) leaching solution 10. The obtained calcium depleted iron and vanadium containing materi-al 13 is then subjected to roasting 5 under elevated temperature, typically in the presence of salt(s), to obtain a roasted slag 20 which comprises iron and vanadi-um. Calcium rich leaching solution 9 obtained from the calcium removal stage 1 is subjected to calcium precipitation 2 by feeding a carbon dioxide containing gas 11 into the calcium rich leaching solution to precipitate calcium carbonate (CaCO3) 12 and to obtain a calcium poor leaching solution 10 which is recirculated to the calcium removal stage 1. The roasted slag 20 which comprises iron and vanadium is further subjected to hydrometallurgical treatment 6 to obtain a stream com-prising vanadium 22 and rejected material 21. The stream comprising the desired valuable metals 22 is then subjected to aluminothermic reduction treatment 7 to obtain ferrovanadium 23.
EXAMPLES
5 The examples for conventional and Ca-removed material are calculat-ed with the same assumptions. V production (V content in hot metal) is fixed to 5000 tpa. V-yield is fixed to 90%. In examples, preheating/prereduction of the feed material and the availability of the furnace are not taken into account.
Tem-peratures of tapped hot metal, tapped slag and furnace gas are fixed.
Metallurgical in coke is used as a carbon reductant in the calculation. The electric and heat losses in electric furnace are not taken into account, because they depend on the select-ed furnace type, furnace size and operating parameters. Also in the examples it is assumed that the material is fed as a fine material into the furnace (pelletizing and sintering/hardening/induration changes the energies and mass balances).
The used slag regions in examples are suitable for the process and are selected to minimize the fluxing in the smelting.
In examples 4 to 7 the main feed material to the smelting is treated with calcium removal process. In that process 90% of the calcium containing compounds is removed from the feed material. The feed material is not altered in any other way.
Reference example 1 In the conventional process Ca-rich material is fed directly into the furnace with quartz and carbon reductant. The slag region is mainly wollastonite (can be also similar areas). The total feed rate into furnace is 49.8 t/h and the to-tal need for fluxes is 12 t/h. The electric power is 48 MW (excl. losses). The ener-gy consumption is 6724 kWh/t of hot metal. Slag/metal ratio is 4.4. The produc-tion of hot metal is 7.1 t/h and for slag is 31 t/h. The content of V and Si in hot metal is 8.1 and 10.9%, respectively.
Reference example 2 In the conventional process Ca-rich material is fed directly into the furnace with quartz, olivine and carbon reductant. The slag region is mainly mer-winite (can be also similar areas). The total feed rate into furnace is 54.8 t/h and the total need for fluxes is 16.9 t/h. The electric power is 52 MW (excl.
losses).
The energy consumption is 6809 kWh/t of hot metal. Slag/metal ratio is 4.6.
The production of hot metal is 7.7 t/h and for slag is 35 t/h. The content of V
and Si in hot metal is 7.5 and 9.6%, respectively.
Reference example 3 In the conventional process Ca-rich material is fed directly into the furnace with quartz, olivine, bauxite and carbon reductant. The slag region is mainly spinel (can be also similar areas). The total feed rate into furnace is 72.0 t/h and the total need for fluxes is 33.0 t/h. The electric power is 67 MW (excl.
loss-es). The energy consumption is 8367 kWh/t of hot metal (excl. losses).
Slag/metal ratio is 5.8. The production of hot metal is 8.1 t/h and for slag is 47 t/h.
The con-tent of V and Si in hot metal is 7.1 and 9.0%, respectively.
Example 4 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with Ca-rich material and carbon reductant. The slag re-gion is mainly melilite (can be also similar areas). The total feed rate into furnace is 23.7 t/h and the total need for fluxes is 7.0 t/h, where 7.0 t/h (all of the fluxes) is the original feed material bypassing the Ca removal process. The electric power is 24 MW (excl. losses). The energy consumption is 3753 kWh/t of hot metal (excl.
losses). Slag/metal ratio is 1.6. The production of hot metal is 6.5 t/h and for slag is 10 t/h. The content of V and Si in hot metal is 8.8 and 3.3%, respectively.
Example 5 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with Ca-rich material, quartz, olivine and carbon reductant.
The slag region is mainly merwinite (can be also similar areas). The total feed rate into furnace is 31.8 t/h and the total need for fluxes is 17 t/h, where 12.9 t/h is the original feed material bypassing the Ca removal process. The electric power is MW (excl. losses). The energy consumption is 4489 kWh/t of hot metal (excl.
losses). Slag/metal ratio is 2.3. The production of hot metal is 6.8 t/h and for slag is 16 t/h. The content of V and Si in hot metal is 8.4 and 4.7%, respectively.
Example 6 30 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with dolomite, bauxite and carbon reductant. The slag re-gion is mainly spinel (can be also similar areas). The total feed rate into furnace is 35.2 t/h and the total need for fluxes is 13.3 t/h, where 0 t/h is the original feed material bypassing the Ca removal process. The electric power is 35 MW (excl.
losses). The energy consumption is 5314 kWh/t of hot metal (excl. losses).
Slag/metal ratio is 2.3. The production of hot metal is 6.5 t/h and for slag is 15 t/h.
The content of V and Si in hot metal is 8.8 and 3.4 %, respectively.
Example 7 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with Ca-rich material, dolomite, iron pellets/concentrate and carbon reductant. In the example the Si in hot metal is diluted to 1.0%
(the feed rate of the iron bearing material is 26 t/h). The slag region is mainly merwin-ite (can be also similar areas). The total feed rate into furnace is 59.8 t/h and the total need for fluxes is 11.0 t/h, where 4 t/h is the original feed material bypass-ing the Ca removal process. The electric power is 71 MW (excl. losses). The ener-gy consumption is 2965 kWh/t of hot metal (excl. losses). Slag/metal ratio is 0.6.
The production of hot metal is 23.9 t/h and for slag is 14 t/h. The content of V and Si in hot metal is 2.4 and 1.0%, respectively.
Reference example 8 Conventional roasting of such material is done with salt roasting. The purpose of the roasting is to produce water-soluble vanadium compound. The conventional feed material comes from the smelting and converting process and contains very small amounts of calcium. Typically process requires less than 1%
of free lime in the feed material. The amount of salt fed to the roasting is propor-tional to the vanadium content of the feed material to roasting. Salts used in the roasting are conventionally NaCl, Na2C 03 and Na2S 04.
The calcium containing feed material is not suitable to the convention-al salt roasting process since a high calcium concentration causes formation of vanadium bearing calcium compounds that are insoluble to the subsequent leach-ing process. Vanadium that is not leached cannot be recovered in the leaching process. Accordingly in the presence of calcium the vanadium losses in the subse-quent leaching stage are too high to reach economical process.
Example 9 In accordance with the present process, when calcium depleted mate-rial is fed to the roasting the calcium content is significantly lower and the losses of vanadium are significantly lower. It has been studied that with slag calcium-vanadium ratio is no higher than 0.42 calculated as CaO and V205 respectively the vanadium recovery of 93% can be achieved in the subsequent leaching process.
This ratio would be achieved with calcium rich feed material used in the previous examples when 97% w/w of calcium is removed in the calcium removal stage.
Conclusions The results of the Examples 1 to 7 are shown in Table 1. As can be seen, the use of calcium removed slag provides lower smelting power require-ment and lower Si level in hot metal. Also slag vs. metal ratio is lower when using calcium removed slag.
Table 1 # Smelting power requirement Slag/metal V in hot metal Si in hot metal MW ratio % %
1 48 4.4 8.1 10.9 2 52 4.6 7.5 9.6 3 67 5.8 7.1 9.0 4 24 1.6 8.8 3.3 5 30 2.3 8.4 4.7 6 35 2.3 8.8 3.4 7 71 0.6 2.4 1.0 It will be obvious to a person skilled in the art that, as the technology advances, the inventive concept can be implemented in various ways. The inven-tion and its embodiments are not limited to the examples described above but may vary within the scope of the claims.
Figure 3 shows a third example of the present process wherein calci-um rich iron containing material further comprising vanadium 8 is subjected to a calcium removal stage 1 accomplished by leaching in a (calcium poor) leaching solution 10. The obtained calcium depleted iron and vanadium containing materi-al 13 is then subjected to a smelting stage 3 under elevated temperature and re-in ducing conditions in the presence of flux material(s) 14 to obtain hot metal 17 which comprises iron and vanadium, slag 15 and evaporated material 16. The calcium rich leaching solution 9 obtained from the calcium removal stage 1 is sub-jected to calcium precipitation 2 by feeding a carbon dioxide containing gas into the calcium rich leaching solution to precipitate calcium carbonate (CaCO3) 12 and to obtain a calcium poor leaching solution 10 which is recirculated to the calcium removal stage 1. Hot metal 17 comprising iron and vanadium obtained from smelting 3 is then subjected to converting 4 to obtain pig iron 18 and slag comprising vanadium and iron 19. The slag 19 is then subjected to roasting 5 per-formed under an elevated temperature, typically in the presence of salt(s), to ob-tam n roasted slag 20 which comprises vanadium and iron and which is then fur-ther subjected to hydrometallurgical treatment 6 to obtain a stream comprising iron and vanadium 22 and rejected material 21. The stream comprising iron and vanadium 22 is then subjected to an aluminothermic reduction treatment 7 to obtain ferrovanadium 23.
Figure 4 shows a fourth example of the present process wherein calci-um rich iron containing material further comprising vanadium 8 is subjected to a calcium removal stage 1 accomplished by leaching in a (calcium poor) leaching solution 10. The obtained calcium depleted iron and vanadium containing materi-al 13 is then subjected to roasting 5 under elevated temperature, typically in the presence of salt(s), to obtain a roasted slag 20 which comprises iron and vanadi-um. Calcium rich leaching solution 9 obtained from the calcium removal stage 1 is subjected to calcium precipitation 2 by feeding a carbon dioxide containing gas 11 into the calcium rich leaching solution to precipitate calcium carbonate (CaCO3) 12 and to obtain a calcium poor leaching solution 10 which is recirculated to the calcium removal stage 1. The roasted slag 20 which comprises iron and vanadium is further subjected to hydrometallurgical treatment 6 to obtain a stream com-prising vanadium 22 and rejected material 21. The stream comprising the desired valuable metals 22 is then subjected to aluminothermic reduction treatment 7 to obtain ferrovanadium 23.
EXAMPLES
5 The examples for conventional and Ca-removed material are calculat-ed with the same assumptions. V production (V content in hot metal) is fixed to 5000 tpa. V-yield is fixed to 90%. In examples, preheating/prereduction of the feed material and the availability of the furnace are not taken into account.
Tem-peratures of tapped hot metal, tapped slag and furnace gas are fixed.
Metallurgical in coke is used as a carbon reductant in the calculation. The electric and heat losses in electric furnace are not taken into account, because they depend on the select-ed furnace type, furnace size and operating parameters. Also in the examples it is assumed that the material is fed as a fine material into the furnace (pelletizing and sintering/hardening/induration changes the energies and mass balances).
The used slag regions in examples are suitable for the process and are selected to minimize the fluxing in the smelting.
In examples 4 to 7 the main feed material to the smelting is treated with calcium removal process. In that process 90% of the calcium containing compounds is removed from the feed material. The feed material is not altered in any other way.
Reference example 1 In the conventional process Ca-rich material is fed directly into the furnace with quartz and carbon reductant. The slag region is mainly wollastonite (can be also similar areas). The total feed rate into furnace is 49.8 t/h and the to-tal need for fluxes is 12 t/h. The electric power is 48 MW (excl. losses). The ener-gy consumption is 6724 kWh/t of hot metal. Slag/metal ratio is 4.4. The produc-tion of hot metal is 7.1 t/h and for slag is 31 t/h. The content of V and Si in hot metal is 8.1 and 10.9%, respectively.
Reference example 2 In the conventional process Ca-rich material is fed directly into the furnace with quartz, olivine and carbon reductant. The slag region is mainly mer-winite (can be also similar areas). The total feed rate into furnace is 54.8 t/h and the total need for fluxes is 16.9 t/h. The electric power is 52 MW (excl.
losses).
The energy consumption is 6809 kWh/t of hot metal. Slag/metal ratio is 4.6.
The production of hot metal is 7.7 t/h and for slag is 35 t/h. The content of V
and Si in hot metal is 7.5 and 9.6%, respectively.
Reference example 3 In the conventional process Ca-rich material is fed directly into the furnace with quartz, olivine, bauxite and carbon reductant. The slag region is mainly spinel (can be also similar areas). The total feed rate into furnace is 72.0 t/h and the total need for fluxes is 33.0 t/h. The electric power is 67 MW (excl.
loss-es). The energy consumption is 8367 kWh/t of hot metal (excl. losses).
Slag/metal ratio is 5.8. The production of hot metal is 8.1 t/h and for slag is 47 t/h.
The con-tent of V and Si in hot metal is 7.1 and 9.0%, respectively.
Example 4 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with Ca-rich material and carbon reductant. The slag re-gion is mainly melilite (can be also similar areas). The total feed rate into furnace is 23.7 t/h and the total need for fluxes is 7.0 t/h, where 7.0 t/h (all of the fluxes) is the original feed material bypassing the Ca removal process. The electric power is 24 MW (excl. losses). The energy consumption is 3753 kWh/t of hot metal (excl.
losses). Slag/metal ratio is 1.6. The production of hot metal is 6.5 t/h and for slag is 10 t/h. The content of V and Si in hot metal is 8.8 and 3.3%, respectively.
Example 5 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with Ca-rich material, quartz, olivine and carbon reductant.
The slag region is mainly merwinite (can be also similar areas). The total feed rate into furnace is 31.8 t/h and the total need for fluxes is 17 t/h, where 12.9 t/h is the original feed material bypassing the Ca removal process. The electric power is MW (excl. losses). The energy consumption is 4489 kWh/t of hot metal (excl.
losses). Slag/metal ratio is 2.3. The production of hot metal is 6.8 t/h and for slag is 16 t/h. The content of V and Si in hot metal is 8.4 and 4.7%, respectively.
Example 6 30 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with dolomite, bauxite and carbon reductant. The slag re-gion is mainly spinel (can be also similar areas). The total feed rate into furnace is 35.2 t/h and the total need for fluxes is 13.3 t/h, where 0 t/h is the original feed material bypassing the Ca removal process. The electric power is 35 MW (excl.
losses). The energy consumption is 5314 kWh/t of hot metal (excl. losses).
Slag/metal ratio is 2.3. The production of hot metal is 6.5 t/h and for slag is 15 t/h.
The content of V and Si in hot metal is 8.8 and 3.4 %, respectively.
Example 7 In accordance with the present process, Ca removed material is fed di-rectly into the furnace with Ca-rich material, dolomite, iron pellets/concentrate and carbon reductant. In the example the Si in hot metal is diluted to 1.0%
(the feed rate of the iron bearing material is 26 t/h). The slag region is mainly merwin-ite (can be also similar areas). The total feed rate into furnace is 59.8 t/h and the total need for fluxes is 11.0 t/h, where 4 t/h is the original feed material bypass-ing the Ca removal process. The electric power is 71 MW (excl. losses). The ener-gy consumption is 2965 kWh/t of hot metal (excl. losses). Slag/metal ratio is 0.6.
The production of hot metal is 23.9 t/h and for slag is 14 t/h. The content of V and Si in hot metal is 2.4 and 1.0%, respectively.
Reference example 8 Conventional roasting of such material is done with salt roasting. The purpose of the roasting is to produce water-soluble vanadium compound. The conventional feed material comes from the smelting and converting process and contains very small amounts of calcium. Typically process requires less than 1%
of free lime in the feed material. The amount of salt fed to the roasting is propor-tional to the vanadium content of the feed material to roasting. Salts used in the roasting are conventionally NaCl, Na2C 03 and Na2S 04.
The calcium containing feed material is not suitable to the convention-al salt roasting process since a high calcium concentration causes formation of vanadium bearing calcium compounds that are insoluble to the subsequent leach-ing process. Vanadium that is not leached cannot be recovered in the leaching process. Accordingly in the presence of calcium the vanadium losses in the subse-quent leaching stage are too high to reach economical process.
Example 9 In accordance with the present process, when calcium depleted mate-rial is fed to the roasting the calcium content is significantly lower and the losses of vanadium are significantly lower. It has been studied that with slag calcium-vanadium ratio is no higher than 0.42 calculated as CaO and V205 respectively the vanadium recovery of 93% can be achieved in the subsequent leaching process.
This ratio would be achieved with calcium rich feed material used in the previous examples when 97% w/w of calcium is removed in the calcium removal stage.
Conclusions The results of the Examples 1 to 7 are shown in Table 1. As can be seen, the use of calcium removed slag provides lower smelting power require-ment and lower Si level in hot metal. Also slag vs. metal ratio is lower when using calcium removed slag.
Table 1 # Smelting power requirement Slag/metal V in hot metal Si in hot metal MW ratio % %
1 48 4.4 8.1 10.9 2 52 4.6 7.5 9.6 3 67 5.8 7.1 9.0 4 24 1.6 8.8 3.3 5 30 2.3 8.4 4.7 6 35 2.3 8.8 3.4 7 71 0.6 2.4 1.0 It will be obvious to a person skilled in the art that, as the technology advances, the inventive concept can be implemented in various ways. The inven-tion and its embodiments are not limited to the examples described above but may vary within the scope of the claims.
Claims (15)
1. A process for recovering metal(s) from calcium rich iron containing material, comprising (a) leaching calcium one or more times from said calcium rich iron containing material to obtain a calcium depleted iron containing material; and (b) subjecting the calcium depleted iron containing material to pyro-metallurgical treatment to recover metal(s) from said calcium depleted iron con-taining material.
2. A process as claimed in claim 1, wherein the calcium rich iron con-taining material is slag, in particular LD slag.
3. A process as claimed in claim 1 or 2, wherein the calcium rich iron containing material comprises at least 20% w/w, preferably at least 25% w/w, more preferably at least 30% w/w, calcium.
4. A process as claimed in any one of claims 1 to 3, wherein the calcium containing material comprises at least 5% w/w, preferably at least 10% w/w, more preferably at least 15% w/w, iron.
5. A process as claimed in any one of claims 1 to 4, wherein the calcium rich iron containing material further comprises vanadium.
6. A process as claimed in claim 4, wherein the calcium rich iron con-taining material comprises at least 0.2% w/w, preferably 0.5% w/w, more pref-erably at least 1% w/w, even more preferably at least 1.5% w/w, vanadium.
7. A process as claimed in any one of claims 1 to 6, wherein vanadium and/or iron are recovered from the calcium rich iron containing material.
8. A process as claimed in any one of claims 1 to 7, wherein the pyro-metallurgical treatment (b) is at least smelting or roasting.
9. A process as claimed in claim 8, wherein (b) the calcium depleted iron containing material is subjected to smelting to recover metal(s) from the cal-cium depleted iron containing material.
10. A process as claimed in claim 8 or 9, wherein (b) the calcium de-pleted material is subjected to roasting to recover metal(s) from the calcium de-pleted material.
11. A process as claimed in any one of claims 1 to 10, wherein the pro-cess further comprises (d) bubbling carbon dioxide containing gas into the calci-um rich leaching solution obtained from stage (a) to precipitate calcium car-bonate and thus to remove calcium from said calcium rich leaching solution to obtain a regenerated calcium poor leaching solution; and (e) recycling the regen-erated calcium poor leaching solvent to stage (a).
12. A process as claimed in claim 10, wherein before stage (d) the cal-cium rich leaching solution is (c) first filtered to remove residual calcium rich iron containing material from said calcium rich leaching solution.
13. A process as claimed in any one of claims 1 to 12, wherein the leaching solutions for leaching calcium from the calcium containing material in stage (a) is selected from the group consisting of acetic acid, nitric acid, propionic acid, aqueous solutions of ammonium salts, such as aqueous solution of ammoni-um acetate (CH3COONH4), ammonium chloride (NH4CI) or ammonium nitrate (NH4NO3).
14. A process as claimed in any one of claims 1 to 13, wherein the amount of calcium in the calcium depleted iron containing material is below 25%
w/w, preferably below 20% w/w, more preferably below 15% w/w, even more preferably below 10% w/w, most preferably below 1% w/w.
w/w, preferably below 20% w/w, more preferably below 15% w/w, even more preferably below 10% w/w, most preferably below 1% w/w.
15. A process for recovering vanadium from LD slag, comprising (o) providing LD slag;
(i) leaching calcium one or more times from said LD slag to obtain cal-cium depleted LD slag; and (ii) subjecting the calcium depleted LD slag to pyrometallurgical treatment to recover iron and vanadium from the calcium depleted LD slag.
(i) leaching calcium one or more times from said LD slag to obtain cal-cium depleted LD slag; and (ii) subjecting the calcium depleted LD slag to pyrometallurgical treatment to recover iron and vanadium from the calcium depleted LD slag.
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