CN108779512A - Metal is recycled from rich calcium material - Google Patents
Metal is recycled from rich calcium material Download PDFInfo
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- CN108779512A CN108779512A CN201680083696.6A CN201680083696A CN108779512A CN 108779512 A CN108779512 A CN 108779512A CN 201680083696 A CN201680083696 A CN 201680083696A CN 108779512 A CN108779512 A CN 108779512A
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- Prior art keywords
- calcium
- iron
- bearing materials
- dilution
- stage
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- 239000011575 calcium Substances 0.000 title claims abstract description 162
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 149
- 239000000463 material Substances 0.000 title claims abstract description 139
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 107
- 238000000034 method Methods 0.000 claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 53
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical group [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000010790 dilution Methods 0.000 claims abstract description 39
- 239000012895 dilution Substances 0.000 claims abstract description 39
- 238000012545 processing Methods 0.000 claims abstract description 23
- 238000009853 pyrometallurgy Methods 0.000 claims abstract description 22
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 41
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- 238000002386 leaching Methods 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 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
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 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
- 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
- 239000002904 solvent Substances 0.000 claims 1
- 230000004907 flux Effects 0.000 description 22
- 239000002893 slag Substances 0.000 description 19
- 239000003638 chemical reducing agent Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 239000010970 precious metal Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 241001062472 Stokellia anisodon Species 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000003723 Smelting Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 239000010450 olivine Substances 0.000 description 4
- 229910052609 olivine Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-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
- 239000000395 magnesium oxide Substances 0.000 description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 2
- 229910001719 melilite Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds 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
- 239000000378 calcium silicate Substances 0.000 description 1
- 229960003340 calcium silicate Drugs 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 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
- 238000010891 electric arc Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
Abstract
Provided herein is the method that one kind recycling one or more metals from rich calcium iron-bearing materials (8), include (a) from the rich calcium iron-bearing materials (8) it is one or many leach (1) calcium and obtain the iron-bearing materials (13) of calcium dilution；(b) make the iron-bearing materials (13) of the calcium dilution that pyrometallurgy processing (3) is subjected to recycle one or more metals (17) from the iron-bearing materials (13) of the calcium dilution.
Description
Invention field
The present invention relates to precious metals are recycled from rich calcium iron-bearing materials by pyrometallurgy processing, and more particularly relate to
And it is included in the method for going deliming from rich calcium iron content raw material before pyrometallurgy processing.
Background of invention
Some steel mills use the iron ore containing vanadium He other residual metals.During process for making these metals and its
His nonferrous metal oxides are usually finally in clinker.The environmentally harmful metal is had been demonstrated since this clinker contains
The fact that oxide residue, is usually filled and is not used as product.The usual manner for recycling these precious metals is to make
The clinker is subjected to melting.
Most of ferriferous oxides and barium oxide (together with other trace metal of alloying) exist during smelting technology
Reducing agent (be usually carbon containing anthracite, coke or metallicity reducing agent, usually Al, FeSi or any other reducing substances)
In the presence of be reduced to metal phase.Usual melting container is electric arc furnaces (alternating current or direct current type).During smelting technology
Other unreduced oxides form clinker, and calcium oxide keeps the liquidus temperature of clinker high in this clinker, and for melting
Clinker can need the up to 24%w/w silica flux that the total solid of stove is fed.This amount reflect flux mixture only by
The case where quartz composition, and the calcium content of feed material is calculated as 45%w/w by CaO.
The disadvantage one of related with flux material is used is the impurity that is generated by flux material finally in the product of acquisition.
In this case, metallic product silicone content will be higher when using silica flux.This is because with metal is formed by
Amount be input in stove compared to higher silica, the flux amount no matter used, it is generally both held at phase same level.Usually supply
It should be reported as metal phase to the silicon of the percentage of some in system.Although therefore forming component when the tonnage for inputting silicon is higher
Residual metallic keeps identical, but metal silicone content is equally higher.
Metal phase from melting goes to step of converting, and vanadium and other precious metals are by selectively oxygen in step of converting
Turn to clinker.Further use salt calcination process clinker.Further (particularly with vanadium) forms insoluble salt to calcium in salt roasting, if
Calcium is not removed to enough levels in procedure of processing before, this causes the loss in the following hydrometallurgical process stage.
Invention briefly describes
Therefore the object of the present invention is to provide the method for recycling one or more precious metals from rich calcium iron-bearing materials, with
Just overcome problem above.It is achieved the object of the present invention by being characterized in that the method described in independent claims.The present invention
Preferred embodiment be disclosed in the dependent claims.
The present invention is based on realizations beyond expectation：It is removed before pyrometallurgy processing by leaching from rich calcium iron content raw material
Calcium keeps pyrometallurgy processing more effective.It goes deliming to reduce the liquidus temperature of material in melting from material and therefore reduces molten
The aequum of agent material, or even with flux material reducing agent.The result is that melting period inlet amount, remaining slag amount and energy
Amount consumption significantly reduces.The quality of the product obtained from pyrometallurgy processing can be improved by going deliming also.
The present invention can be additionally used in direct after going deliming in the case of the melting of not explained earlier and step of converting
Supply processing selection of the raw material to roasting.Calcium low-level in this way be can reach after going deliming to avoid excessive in roasting
Form insoluble calcium salt.
Another benefit of this method is that calcium removal step eliminates the hydroxide combined with calcium or carbonate such as Ca
(OH)2And CaCO3.Consumed it reduce capacity of furnace and reducing agent and make the pressure of stove control and gas treatment more it is simple therefore more
Safety.In conventional smelting technology if in external storing furnace slag, predrying only removes free water at 200 DEG C and some are crystallized
Water, all hydroxide and carbonate are left to stove charging.
Brief Description Of Drawings
Hereinafter, the present invention is more fully described by preferred embodiment in refer to the attached drawing, wherein
Fig. 1 shows first example of this method；
Fig. 2 shows second example of this method；
Fig. 3 shows the third example of this method；
Fig. 4 shows the 4th example of this method.
Detailed description of the Invention
Provided herein is the methods for recycling one or more metals from rich calcium iron-bearing materials, including
(a) from the rich calcium iron-bearing materials it is one or many leach calcium and obtain the iron-bearing materials of calcium dilution；With
(b) make the iron-bearing materials of the calcium dilution be subjected to pyrometallurgy processing to come from the iron-bearing materials of calcium dilution recycling one
Kind or various metals.
Term " rich calcium iron-bearing materials " refers to the material comprising calcium, iron and other optional one or more precious metals
Material.Other described precious metals are typically at least vanadium.Usually richness calcium iron-bearing materials include at least 20%w/w, particularly at least
25%w/w, more particularly at least 30%w/w, even more particularly at least 40%w/w calcium.Calcium is usually as CaO, Ca (OH)2、
CaCO3, calcium-silicate and/or other calcium containing compounds exist.Usually richness calcium iron-bearing materials include at least 5%w/w, particularly extremely
Few 10%w/w, more particularly at least 15%w/w iron.Particularly rich calcium iron-bearing materials include from 5 to 60%w/w iron.Tie Tong often makees
For Fe3O4、Fe2O3, FeO, metallicity Fe and/or ferrosilicate exist.
Particularly rich calcium iron-bearing materials also include vanadium, typically at least 0.2%w/w, particularly at least 0.5%w/w, particularly
Ground at least 1%w/w, even more particularly at least 1.5%w/w.Vanadium usually as one or more barium oxides (in particular
V2O5) exist.
The representative instance for being suitable for the rich calcium iron-bearing materials handled by this method is clinker, such as steel converter clinker or steel-making
Clinker.The particular example of the richness calcium iron-bearing materials is LD clinkers, also known as basic oxygen furnace (BOS) or LD- turn
The pig iron is processed into the by-product of the Linz-Donawitz process (Linz-Donawitz process) of crude steel by stove clinker.
The particular example of this method is the method for recycling iron and vanadium from LD clinkers, including
(o) LD clinkers are provided；
(i) from the LD clinkers it is one or many leach calcium and obtain the LD clinkers of calcium dilution；With
(ii) make the LD clinkers of the calcium dilution that pyrometallurgy processing is subjected to recycle iron and vanadium from the LD clinkers of the calcium dilution.
As term " comprising " herein and hereafter used describes signified project, such as the work including restriction in a non-limiting manner
This method in skill stage is at least made of the stage, but can include when needed additionally other operation stages.However, including
The method of the operation stage of restriction can be only made of the operation stage.
According to this method, present invention richness calcium iron-bearing materials are subjected to (a) leaching before (b) one or many pyrometallurgy processing
Out deliming is gone from material.
Fig. 1 shows first example of this method, wherein rich calcium iron-bearing materials 8 are removed the stage 1 supplied to calcium, wherein passing through
The material 13 and rich calcium leachate 9 for completing calcium removal to obtain calcium dilution are leached in (poor calcium) leachate 10.It then will be such
The iron-bearing materials 13 of the calcium dilution of acquisition are supplied to pyrometallurgy processing stage, it is in raised temperature and to go back in this example
The smelt stage 3 carried out under old terms and in the presence of flux material 14, to obtain the heat gold comprising required precious metals
Belong to the material 16 of 17, clinker 15 and evaporation.By the way that carbonated gas 11 is supplied to rich calcium leachate so that carbonic acid is precipitated
Calcium (CaCO3) 12 and obtain then be recycled back to calcium removal the stage 1 poor calcium leachate 10, make from calcium removal the stage 1 obtain
Rich calcium leachate 9 be subjected to calcium be precipitated 2.
Fig. 2 shows second example of this method.Rich calcium iron-bearing materials 8 are subjected to the calcium removal stage 1 in method shown in Fig. 2,
The calcium removal stage 1 is completed with the iron-bearing materials 13 for obtaining calcium dilution and rich calcium leachate by being leached in (poor calcium) leachate 10
9.Then the iron-bearing materials 13 of the calcium dilution so obtained are supplied to pyrometallurgy processing stage, it is to rise in this example
The firing stage 5 usually carried out in the presence of one or more salt at high temperature, to obtain comprising required precious metals
Roasting slag 20.By the way that carbonated gas 11 is supplied to rich calcium leachate to obtain calcium carbonate (CaCO3) 12 Hes
It is then recirculated to the poor calcium leachate 10 in calcium removal stage 1, the rich calcium leachate 9 obtained from the calcium removal stage 1 is made to be subjected to
Calcium is precipitated 2.
The similarly suitable leachate in the stage (i) for going deliming from rich calcium iron-bearing materials is neutralized in the stage (a)
Those leachates e.g. selected from the following：Acetic acid, nitric acid, propionic acid, ammonium salt aqueous solution such as ammonium acetate (CH3COONH4), ammonium chloride
(NH4) or ammonium nitrate (NH Cl4NO3) aqueous solution.It is preferred that leachate of the present invention is saline solution, especially ammonium salt aqueous solution is more special
Other ground ammonium acetate (CH3COONH4), ammonium chloride (NH4) or ammonium nitrate (NH Cl4NO3) aqueous solution, most preferably ammonium chloride
(NH4Cl).The salinity of saline solution is usually from 0.2 to 8M, and preferably 0.5 to 5M, more preferable 0.5 to 2M.
It neutralizes and is similarly leached in the stage (i) usually from 0 to 100 DEG C, preferably from 10 to 70 in calcium removal stage (a)
DEG C, more preferably from carrying out at a temperature of 20 to 70 DEG C.Most preferably, it is soaked using saline solution at a temperature of 20 to 60 DEG C
Go out.The required crystal form that calcium carbonate is precipitated has an impact extraction temperature, because different crystal forms is analysed at different temperatures
Go out and solution is cycle.It need not be cooled down before leaching stage or heated solution.
One or many leachings can be similarly carried out in the stage (i) in calcium removal stage (a) neutralization.
Because carrying out neutralizing the calcium removal similarly in the stage (i) in the stage (a) to be reduced to pyrometallurgy to handle rank
Section (b) and similarly to the calcium concentration in the charging of stage (ii), and some calcium are needed to reduce the liquid of clinker in melting
Liquidus temperature, so the problem of being optimization below：Whether in calcium removal stage (a) the similarly only part in the stage (i) is neutralized
It goes deliming and/or whether directly supplies some rich calcium iron-bearing materials in the case where no calcium removes to go melting, or whether in calcium
Deliming is gone in the removal stage (a) and in the similarly stage (i) as much as possible.Exist in rich calcium iron-bearing materials it is preferred that eliminating
At least calcium of 60%w/w.
When need only partly go deliming when, preferably in the stage (a) similarly with the stage (i) in carry out single phase leaching
Go out, and is preferably removed from rich calcium iron-bearing materials from 60 to 90%w/w, the calcium more preferably from 65 to 85%w/w.Calcium in the case
The amount of calcium is preferably smaller than 25%w/w in the iron-bearing materials of dilution, more preferably less than 20%w/w, even more preferably less than 17%w/
w。
It is when needing to go deliming as much as possible, then preferred to repeat to leach until eliminate at least 70%w/w, more preferably from
75% to 100%w/w, even more preferably from 80% to 99% the calcium being present in rich calcium iron-bearing materials.Calcium in the case
The amount of calcium is preferably smaller than 20%w/w in the iron-bearing materials of dilution, more preferably less than 15%w/w, even more preferably less than 10%w/
W, more preferably less than 1%w/w.Usually when needing to go deliming as much as possible, calcium leaching stage (a) or (i) twice is carried out.This
The leaching stage number that text is pointed out is directed to leaching stage (a) and similarly time to the stage (i) using new (poor calcium) leachate
Number.Therefore, several leaching stages can also be carried out as individual leaching stage, wherein in the leaching container continuously arranged or
Single leach is leached in container (it is continuously refilled with new (poor calcium) leachate).
As discussed above in the context of the first and second examples, in step (a) and similarly step (i), remove
Except the iron-bearing materials of calcium dilution, the used leachate containing the calcium dissolved from rich calcium iron-bearing materials is obtained.Herein and
Used leachate described below is also called rich calcium leachate.If necessary to recycle and reuse the used leaching
Go out liquid, then should go deliming from used leachate to obtain poor calcium leachate.This is preferably completed by being precipitated.
The representative instance that calcium is precipitated from rich calcium leachate is carbonation.This can be by accomplished below：(c) optionally first
Used rich calcium leachate is first filtered to come from the rich remaining rich calcium iron-bearing materials of calcium leachate removal；(d) it is soaked to rich calcium
Go out in liquid to blast carbonated gas (especially carbon dioxide) calcium carbonate is precipitated simultaneously therefore from the rich calcium leachate
Deliming is gone to obtain the poor calcium leachate of regeneration.Then the regeneration poor calcium leachate difference (e) can be recycled to the stage (a) or
(i).The carbon dioxide needed in stage (d) can for example be obtained from flue gas or other sources.The temperature of carbonation depends on
The required crystal form of the calcium carbonate of precipitation.Different crystal forms are precipitated at different temperatures, such as aragonite can be at 60 DEG C
It is precipitated.
After going deliming from material, the iron-bearing materials of calcium dilution is made to be subjected to pyrometallurgy processing stage (b) or (ii).?
Before the iron-bearing materials of calcium dilution are supplied to pyrometallurgy processing stage (b) or (ii), containing for the calcium dilution is preferably dried
Iron material.
This pyrometallurgy processing stage (b) or (ii) can be known to technical staff and to be found to be suitable for poor from the calcium of processing
Any one or more of pyrometallurgy processing of precious metals needed for the iron-bearing materials recycling of change.Usual pyrometallurgy handle to
It is melting or roasting less.It is preferred that the material of calcium dilution is made to be subjected at least melting.
Due to calcium removal stage (a) or (i) before, compared with untreated rich calcium iron-bearing materials, respectively to pyrogenic process smelting
The quality stream smaller of the iron-bearing materials of the calcium dilution of golden stage (b) or (ii), because calcium is the main member in rich calcium iron-bearing materials
One of element.This makes stove size reduce and reduces required electric power in pyrometallurgy processing procedure and/or productivity is made to improve.
In addition, the liquid of the mixture of the iron-bearing materials of the calcium dilution and optionally the desired amount of untreated rich calcium iron-bearing materials
Liquidus temperature is lower compared with respectively untreated rich calcium iron-bearing materials.Therefore the use of flux material is minimized.When making material
Being subjected to the stage (b), this is especially relevant when neutralizing the melting similarly in the stage (ii).
Reach required slag zone need add calcareous material in the case of, can also add to the fire metallurgy process stage
Add some untreated rich calcium iron-bearing materials.
According to this method, flux material can be used for reaching correct slag zone in smelt stage.It is preferred that the flux added
Quantity of material is less than 45%w/w (in the case where no calcium removal is handled in addition to initial rich calcium iron content charging), more preferably small
Flux is not needed in 15%w/w and in some cases.Possible flux material include conventional flux materials for example those be selected from
Lime, wollastonite, alumina, quartz and olivine, and include SiO2, CaO, MgO and/or Al2O3Other materials.
In addition, iron and/or iron ball group can be added when needed or comprising FeO, Fe3O4、Fe2O3And/or V2O5It is any its
His material or the other materials containing a large amount of iron and/or vanadium.It is preferred that selecting slag zone in melting to make in melting slag making most
It is few.Following slag zone is possible：Such as merwinite, melilite (mellilite), silicoglaserite, akermanite, magnesium olive
Stone, spinelle, monticellite, pseudo- wollastonite, pyroxene, dicalcium silicate, periclase, anorthite, cordierite, mullite and other
Similar region.
It, can be in skill when making the iron-bearing materials of calcium dilution be subjected in the stage (b) and the melting in the similarly stage (ii)
Under the conditions of art personnel are known i.e. as described above at raised temperature and reducing condition and optional one or more molten
Smelt stage is carried out in the presence of agent material.Coke is usually used as carbonaceous reducing agent in smelt stage；However carbonaceous reducing agent can be to appoint
What his carbon containing reducer, such as anthracite.Reducing agent can also be metallic reducing agent, and the use of metallic reducing agent influences energy and disappears
Consumption and feed rate.It can be converted after melting when needing really.When needing really after melting and optional conversion
It can also roast.
In the case where iron-bearing materials are supplied directly into roasting technique by no sintering stage, if iron-bearing materials include
Excessive calcium then its can form the insoluble calcium salt containing vanadium.It is minimized to make to be formed such salt, needs to remove the stage in calcium
(a) or (i) deliming is gone as much as possible from untreated rich calcium iron-bearing materials in.It is subjected to the stage when making the iron-bearing materials of calcium dilution
(b) (i.e. at elevated temperatures, logical under the conditions of can be known to technical staff when neutralizing the roasting similarly in the stage (ii)
Often in the presence of one or more salt) firing stage is carried out, to obtain roasting slag.The salt that firing stage uses is routinely
NaCl、Na2CO3And Na2SO4。
It is preferred that the iron-bearing materials of calcium dilution are supplied to pyrometallurgy stage (b) or (ii) with thin material forms.Can also it lead to
Any other suitable method known to technical staff is crossed by its pelletizing, sintering and/or pretreatment.
Fig. 3 shows the third example of this method, wherein the also rich calcium iron-bearing materials 8 comprising vanadium is made to be subjected to by (poor calcium)
The calcium removal stage 1 leached and completed in leachate 10.Then the material 13 of the iron content and vanadium that make the calcium dilution of acquisition is subjected to
Smelt stage 3 at raised temperature and reducing condition in the presence of one or more flux materials 14 is obtained comprising iron and vanadium
Thermometal 17, clinker 15 and evaporation material 16.By by carbonated gas 11 be supplied in rich calcium leachate with
Calcium carbonate (CaCO is precipitated3) 12 and obtain be recirculated to calcium removal the stage 1 poor calcium leachate 10, make from calcium remove the stage 1
The rich calcium leachate 9 of acquisition is subjected to calcium and is precipitated 2.Then the thermometal 17 comprising iron and vanadium obtained from melting 3 is made to be subjected to conversion 4
To obtain the pig iron 18 and the clinker 19 comprising vanadium and iron.Then clinker 19 is made to be subjected at elevated temperatures usually a kind of or more
The roasting 5 carried out in the presence of kind salt then also makes it be also subject to hydrometallurgy to obtain the roasting slag 20 comprising vanadium and iron
6 are handled to obtain stream 22 and the obsolete material 21 comprising iron and vanadium.Then the stream 22 comprising iron and vanadium is made to be subjected to aluminothermy also
7 are managed to obtain ferrovanadium 23 in original place.
Fig. 4 shows the 4th example of this method, wherein the also rich calcium iron-bearing materials 8 comprising vanadium is made to be subjected to by (poor calcium)
The calcium removal step 1 for leaching and completing in leachate 10.Then the iron content of the calcium dilution of acquisition and vanadium material 13 is made to be subjected to rising
Roasting 5 at high temperature usually in the presence of one or more salt, to obtain the roasting slag 20 comprising iron and vanadium.Pass through
Carbonated gas 11 is supplied in rich calcium leachate so that calcium carbonate (CaCO is precipitated3) 12 and obtain be recirculated to calcium
The poor calcium leachate 10 in removal stage 1 makes the rich calcium leachate 9 obtained from the calcium removal stage 1 be subjected to calcium and is precipitated 2.Further make
Including the roasting slag 20 of iron and vanadium is subjected to hydrometallurgical process 6 to obtain the stream 22 and obsolete material 21 comprising vanadium.Then
The stream 22 comprising required precious metals is set to be subjected to aluminothermic reduction processing 7 to obtain ferrovanadium 23.
Embodiment
With the identical embodiment for assuming to calculate conventional material and Ca- material removals.V yield (V content in thermometal)
It is fixed as 5000tpa.V yields are fixed as 90%.Do not accounted in embodiment feed material preheating/prereduction and stove can
The property used.The temperature of the thermometal of outflow, the clinker of outflow and furnace gas is fixed.Metallurgical coke is used as the carbonaceous reducing agent in calculating.No
The electrically and thermally loss in electric furnace is considered, because they depend on selected stove type, stove size and operation temperature.Also in embodiment
It is middle to assume material being supplied in stove (pelletizing and sintering/hardening/consolidation change energy and mass balance) with thin material forms.
The slag zone used in embodiment is suitable for this method and is selected for making slag making in melting minimum.
Using the principal feedstock material of calcium removal process melting in embodiment 4-7.In the process from charging material
The calcium containing compound of material removal 90%.Do not change feed material in any other manner.
Comparative example 1
Rich Ca materials and quartz and carbonaceous reducing agent are supplied directly into stove in conventional method.Slag zone is mainly silicon
Lime stone (can also be similar region).To the total feed rate in stove be 49.8t/h and flux aggregate demand is 12t/h.Electric work
Rate is 48MW (loss forecloses).Energy expenditure is 6724kWh/t thermometals.Clinker/metal ratio is 4.4.Thermometal produces
Amount for 7.1t/h and clinker is 31t/h.The content of V and Si is 8.1 and 10.9% respectively in thermometal.
Comparative example 2
Rich Ca materials and quartz, olivine and carbonaceous reducing agent are supplied directly into stove in conventional method.Slag zone
Mainly merwinite (can also be similar region).To the total feed rate in stove be 54.8t/h and flux aggregate demand is
16.9t/h.Electrical power is 52MW (loss forecloses).Energy expenditure is 6809kWh/t thermometals.Clinker/metal ratio is
4.6.Thermometal yield is 7.7t/h and clinker is 35t/h.The content of V and Si is 7.5 and 9.6% respectively in thermometal.
Comparative example 3
Rich Ca materials and quartz, olivine, alumina and carbonaceous reducing agent are supplied directly into stove in conventional method.Clinker
Region is mainly spinelle (can also be similar region).It is 72.0t/h and flux aggregate demand to the total feed rate in stove
For 33.0t/h.Electrical power is 67MW (loss forecloses).Energy expenditure is that 8367kWh/t thermometals (exclude loss
Outside).Clinker/metal ratio is 5.8.Thermometal yield is 8.1t/h and clinker is 47t/h.The content difference of V and Si in thermometal
It is 7.1 and 9.0%.
Embodiment 4
According to this method, the material for removing Ca and richness Ca materials and carbonaceous reducing agent are supplied directly into stove.Slag zone
Mainly melilite (can also be similar region).To the total feed rate in stove be 23.7t/h and flux aggregate demand is
7.0t/h, wherein 7.0t/h (all flux) are the original feed materials for avoiding Ca removal techniques.Electrical power, which is 24MW, (will be lost
It forecloses).Energy expenditure is 3753kWh/t thermometals (loss forecloses).Clinker/metal ratio is 1.6.Thermometal produces
Amount for 6.5t/h and clinker is 10t/h.The content of V and Si is 8.8 and 3.3% respectively in thermometal.
Embodiment 5
According to this method, the material for removing Ca and richness Ca materials, quartz, olivine and carbonaceous reducing agent are supplied directly into stove
In.Slag zone is mainly merwinite (can also be similar region).It is 31.8t/h to the total feed rate in stove and melts
Agent aggregate demand is 17t/h, and wherein 12.9t/h is the original feed material for avoiding Ca removal techniques.Electrical power, which is 30MW, (will be lost
It forecloses).Energy expenditure is 4489kWh/t thermometals (loss forecloses).Clinker/metal ratio is 2.3.Thermometal produces
Amount for 6.8t/h and clinker is 16t/h.The content of V and Si is 8.4 and 4.7% respectively in thermometal.
Embodiment 6
According to this method, the material for removing Ca and dolomite, alumina and carbonaceous reducing agent are supplied directly into stove.Clinker area
Domain is mainly spinelle (can also be similar region).To the total feed rate in stove be 35.2t/h and flux aggregate demand is
13.3t/h, wherein 0t/h are the original feed materials for avoiding Ca removal techniques.Electrical power is 35MW (loss forecloses).
Energy expenditure is 5314kWh/t thermometals (loss forecloses).Clinker/metal ratio is 2.3.Thermometal yield is 6.5t/h
And clinker is 15t/h.The content of V and Si is 8.8 and 3.4% respectively in thermometal.
Embodiment 7
It is according to this method, the material and richness Ca materials, dolomite, iron ball group/concentrate and carbonaceous reducing agent that remove Ca is direct
Supplied in stove.The Si in thermometal is diluted to 1.0% (feed rate of iron-bearing materials is 26t/h) in this embodiment.
Slag zone is mainly merwinite (can also be similar region).It is 59.8t/h and flux to the total feed rate in stove
Aggregate demand is 11.0t/h, and wherein 4t/h is the original feed material for avoiding Ca removal techniques.Electrical power is that 71MW (arranges loss
Except outside).Energy expenditure is 2965kWh/t thermometals (loss forecloses).Clinker/metal ratio is 0.6.Thermometal yield
For 23.9t/h, clinker is 14t/h.The content of V and Si is 2.4 and 1.0% respectively in thermometal.
Comparative example 8
The conventional roasting of this material is carried out using salt roasting.The purpose of roasting is to generate water-soluble vfanadium compound.It is conventional
Feed material is from melting and conversion process and contains very small amount of calcium.Method usually requires to be less than 1% in feed material
Free calcium oxide.Salt amount supplied to roasting is proportional to the feed material content of vanadium of roasting.Salt for roasting is routinely
It is NaCl, Na2CO3And Na2SO4。
Feed material containing calcium is not suitable for conventional salt roasting technique, because high calcium concentration causes to leach insoluble in follow-up
The formation of the calcium compound containing vanadium of technique.The vanadium not leached cannot be recycled in extract technology.Therefore in the presence of calcium and vanadium
The loss of follow-up leaching stage is excessively high and cannot reach economic technique down.
Embodiment 9
According to this method, when by the material supply of calcium dilution, to when roasting, calcium content is significantly lower and the loss of vanadium is aobvious
It writes relatively low.Studies have shown that pressing CaO and V respectively2O5In the case that the clinker calcium of calculating-vanadium ratio is not higher than 0.42, then soaking
Go out in technique and 93% vanadium recycling can be achieved.When eliminating the calcium of 97%w/w in the calcium removal stage, using in embodiment before
The rich calcium feed material used will realize this ratio.
Conclusion
The result of embodiment 1-7 is displayed in Table 1.As can be seen, lower melting work(is provided using the clinker that calcium removes
Lower Si is horizontal in rate demand and thermometal.Equally when the clinker removed using calcium, clinker and metal ratio are relatively low.
Table 1
It will be apparent to one skilled in the art that with advances in technology, can realize this hair in various ways
Bright design.The present invention and its embodiment are not limited to the above embodiments, but can be changed within the scope of the claims.
Claims (15)
1. a kind of method recycling one or more metals from rich calcium iron-bearing materials, including
(a) from the rich calcium iron-bearing materials it is one or many leach calcium and obtain the iron-bearing materials of calcium dilution；With
(b) make the iron-bearing materials of the calcium dilution be subjected to pyrometallurgy processing come from the iron-bearing materials of the calcium dilution recycle it is a kind of or
Various metals.
2. the method as described in claim 1, wherein the richness calcium iron-bearing materials are clinkers, in particular LD clinkers.
3. method as claimed in claim 1 or 2, wherein the richness calcium iron-bearing materials include at least 20%w/w, and preferably at least 25%
W/w, the more preferably at least calcium of 30%w/w.
4. method as described in any one of claims 1 to 3, wherein calcareous material include at least 5%w/w, and preferably at least 10%
W/w, the more preferably at least iron of 15%w/w.
5. such as Claims 1-4 any one of them method, wherein the richness calcium iron-bearing materials also include vanadium.
6. method as claimed in claim 4, wherein the richness calcium iron-bearing materials include at least 0.2%w/w, and preferably at least 0.5%
W/w, more preferably at least 1%w/w, the even more desirably at least vanadium of 1.5%w/w.
7. such as claim 1 to 6 any one of them method, wherein recycling vanadium and/or iron from the richness calcium iron-bearing materials.
8. method as described in any one of claim 1 to 7, the wherein pyrometallurgy processing (b) are at least melting or roasting.
9. method as claimed in claim 8 is come wherein the iron-bearing materials of the calcium dilution (b) is made to be subjected to melting from the calcium dilution
Iron-bearing materials recycle one or more metals.
10. method as claimed in claim 8 or 9, wherein the material of calcium dilution (b) is made to be subjected to roasting the material come from the calcium dilution
Material recycles one or more metals.
11. method as described in any one of claim 1 to 10, wherein this method further include (d) to the richness obtained by the stage (a)
Carbonated gas is blasted in calcium leachate to be obtained calcium carbonate is precipitated and therefore from the rich calcium leachate goes deliming
Regenerate poor calcium leachate；(e) poor calcium leaching solvent will be regenerated and be recycled to the stage (a).
12. method as claimed in claim 10, wherein (c) filters the richness calcium leachate and comes from institute first before the stage (d)
State the remaining rich calcium iron-bearing materials of rich calcium leachate removal.
13. such as claim 1 to 12 any one of them method, wherein the leaching of calcium is leached from calcareous material in the stage (a)
Liquid is selected from the group being made up of：Acetic acid, nitric acid, propionic acid, ammonium salt aqueous solution such as ammonium acetate (CH3COONH4), ammonium chloride
(NH4) or ammonium nitrate (NH Cl4NO3) aqueous solution.
14. such as claim 1 to 13 any one of them method, the amount of calcium is less than 25% wherein in the iron-bearing materials of the calcium dilution
W/w, preferably smaller than 20%w/w, more preferably less than 15%w/w, even more preferably less than 10%w/w, more preferably less than 1%w/w.
15. the method for recycling vanadium from LD clinkers, including
(o) LD clinkers are provided；
(i) from the LD clinkers it is one or many leach calcium and obtain the LD clinkers of calcium dilution；With
(ii) make the LD clinkers of the calcium dilution that pyrometallurgy processing is subjected to recycle iron and vanadium from the LD clinkers of the calcium dilution.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/FI2016/050179 WO2017162901A1 (en) | 2016-03-22 | 2016-03-22 | Recovery of metals from calcium-rich materials |
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| CN108779512A true CN108779512A (en) | 2018-11-09 |
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|---|---|
| EP (1) | EP3433389A4 (en) |
| CN (1) | CN108779512A (en) |
| CA (1) | CA3018028C (en) |
| EA (1) | EA036823B1 (en) |
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| CN109913660A (en) * | 2019-03-18 | 2019-06-21 | 东北大学 | A method of rich vanadium richness iron charge is prepared using v-bearing steel slag |
| CN111560523A (en) * | 2020-06-05 | 2020-08-21 | 昆明理工大学 | New process for purifying and recovering calcium components in vanadium-containing steel slag |
| CN115323199A (en) * | 2021-11-12 | 2022-11-11 | 虔东稀土集团股份有限公司 | Method for recovering rare earth elements |
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| CN109913660A (en) * | 2019-03-18 | 2019-06-21 | 东北大学 | A method of rich vanadium richness iron charge is prepared using v-bearing steel slag |
| CN111560523A (en) * | 2020-06-05 | 2020-08-21 | 昆明理工大学 | New process for purifying and recovering calcium components in vanadium-containing steel slag |
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Also Published As
| Publication number | Publication date |
|---|---|
| ZA201806272B (en) | 2019-07-31 |
| EA201891862A1 (en) | 2019-02-28 |
| WO2017162901A1 (en) | 2017-09-28 |
| EA036823B1 (en) | 2020-12-24 |
| CA3018028C (en) | 2023-09-12 |
| EP3433389A4 (en) | 2019-12-11 |
| EP3433389A1 (en) | 2019-01-30 |
| CA3018028A1 (en) | 2017-09-28 |
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