OA19474A - Process for recycling cobalt-bearing materials. - Google Patents
Process for recycling cobalt-bearing materials. Download PDFInfo
- Publication number
- OA19474A OA19474A OA1201900138 OA19474A OA 19474 A OA19474 A OA 19474A OA 1201900138 OA1201900138 OA 1201900138 OA 19474 A OA19474 A OA 19474A
- Authority
- OA
- OAPI
- Prior art keywords
- cobalt
- slag
- copper
- recovery
- bearing
- Prior art date
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052803 cobalt Inorganic materials 0.000 title claims abstract description 83
- 239000010941 cobalt Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title abstract description 3
- 239000002893 slag Substances 0.000 claims abstract description 69
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 33
- 238000011084 recovery Methods 0.000 claims abstract description 24
- -1 copper-nickel Chemical compound 0.000 claims abstract description 13
- 230000001590 oxidative Effects 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 7
- 241001062472 Stokellia anisodon Species 0.000 claims abstract description 3
- 238000002386 leaching Methods 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 4
- 230000002378 acidificating Effects 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052759 nickel Inorganic materials 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 229910017061 Fe Co Inorganic materials 0.000 description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052904 quartz Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K Lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L Iron(II) sulfate Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000005824 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000003638 reducing agent Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical class [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The present invention concerns the recovery of cobalt from cobalt-bearing materials, in particular from cobalt-bearing lithium-ion secondary batteries, from the spent batteries, or from their scrap. A process is divulged for the recovery of cobalt from cobalt-bearing materials, comprising the steps of: providing a converter furnace, charging slag formers and one or more of copper matte, copper-nickel matte, and impure alloy into the furnace, and injecting an oxidizing gas so as to smelt the charge in oxidizing conditions, thereby obtaining a molten bath comprising a crude metal phase, and a cobalt-bearing slag, and separating the crude metal from the cobaltbearing slag, characterized in that the cobaltbearing materials are charged into the furnace. This process is particularly suitable for recycling cobalt-bearing lithium-ion secondary batteries. Cobalt is concentrated in a limited amount of converter slag, from which it can economically be retrieved, together with other elements such as copper and/or nickel.
Description
The présent invention concerns the recovery of cobalt from cobalt-bearing materials, in particular from cobalt-bearing lithium-ion secondary batteries, from spent batteries or from their scrap.
Using existing large-scale equipment and adding or incorporating the cobalt-bearing materials to the usual feed may provide an interesting alternative to a fully dedicated processing plant. This may be particularly true for cobalt-bearing batteries when the volumes to be treated are limited.
A possible candidate for such a large-scale process is the tandem formed by smelter and converter furnaces as used for treating copper or copper-nickel bearing ores, concentrâtes, or recyclâtes. This more specifïcally comprises: a smelter, operating in mildly oxidizing conditions, producing a copper matte, a copper-nickel matte, or an impure alloy, and a slag; and, a converter for the treatment of the matte or the impure alloy, operating in oxidizing conditions, producing a crude métal and a slag. In représentative industrial operations, the smelter slag will contain significant amounts of iron when operating on ores. The converter slag will contain significant amounts of copper and/or nickel. This slag will normally be recycled to the smelter to ensure high global copper and nickel yields. The smelter slag may be discarded or re-used, e.g. as aggregate in concrète.
WO 2015/096945 proposes a process for the recovery of copper and nickel from lithium-ion batteries by replacing part of a sulfidic smelter charge by lithium-ion batteries or their scrap. Thanks to their high content in carbon and metallic aluminum, they substitute for fuel and reducing agents in the smelter. The nickel in the batteries reports mainly to the matte, together with copper. Both metals can be recovered and separated in further steps, according to known processes. The slag contains iron, and almost no nickel. It is therefore compatible with ecological re-use.
A first disadvantage of the above process is that it is appropriate for materials with a low cobalt content only. Unlike nickel, cobalt reports essentially to the slag, in the form of métal oxide. The précisé distribution amongst the phases dépends upon the redox potential during the process. Cobalt is a highly valuable métal that is preferably recovered with high yields. It is moreover toxic, especially as an oxide. For these two reasons, the amount of cobalt that can be tolerated in the smelter slag is very low, and should preferably remain below 3000 ppm or 0.3%, depending on local législation and the envisaged re-use.
This disadvantage is particularly significant in relation to lithium-ion secondary batteries. While some batteries such as lithium-iron-phosphate (LFP) and lithium-manganese-oxide (LMO) based batteries contain little or no cobalt, most popular batteries such as lithium cobalt oxide (LCO) and lithium-nickel-manganese-cobalt (NMC) based batteries contain about 5 to 20% of cobalt in their cathode.
A second disadvantage of this process is related to the amount of alumina in the smelter slag.
From a practical point of view, up to 6% is considered as an upper bound. Higher concentrations may be used, but the increased melting point and viscosity ofthe slag nécessitâtes a higher working température. This tends to dégradé the energy efficiency and the useful life of the smelter.
This disadvantage is again particularly significant in relation to lithium-ion secondary batteries. Alumina is indeed formed from the aluminum métal présent in batteries, either as support sheets for the électrodes, or as canning material. The relative amount of batteries that can be added to the smelter charge is therefore limited. This results in the dilution ofthe cobalt in the smelter slag.
It is therefore the aim of the présent divulgation to présent an alternative process, which is suitable for recycling cobalt-bearing materials such as most popular lithium secondary batteries.
It has now been found that cobalt, unlike nickel, when introduced directly in a converter, will 25 nearly completely report to the slag.
Moreover, the limit of 6% alumina in the smelter slag, which restricts the quantity of batteries that can be fed to a smelter, can be disregarded in converter slags, as the working température of a converter is usually much higher than that of a smelter. This allows for a higher relative amount of batteries in the feed, and for the concentration of the cobalt in the converter slag.
A converter slag is thus obtained that is potentially much richer in cobalt than what is possible in a smelter slag. This slag also contains residual copper. It should not be recirculated as such to the smelter, but subjected to a process for recovery of cobalt and copper.
Accordingly, a process is divulged for the recovery of cobalt from cobalt-bearing materials, comprising the steps of: providing a converter furnace; charging slag formers and one or more of copper matte, copper-nickel matte, and impure alloy into the furnace, and injecting an oxidizing gas so as to smelt the charge in oxidizing conditions, thereby obtaining a molten bath 5 comprising a crude métal phase, and a cobalt-bearing slag; and, separating the crude métal from the cobalt-bearing slag, characterized in that the cobalt-bearing materials are charged into the furnace.
By converter furnace is meant a furnace suitable to conduct converting operations. This 10 normally implies provisions for the injection of an oxidizing gas such as air, enriched air or pure oxygen, into the melt. Sulfidic sulfur, if présent, is hereby oxidized to sulfur dioxide. By matte are meant sulfidic materials such as copper and nickel sulfides. By impure alloy is meant an alloy containing copper (“black copper”) and/or nickel, and also comprising other éléments such as iron, antimony, and tin. By crude métal is meant a metallic phase such as crude copper or 15 blister copper, optionally containing nickel and other metallic impurities. Slag formers typically comprise lime and silica.
Charging the cobalt-bearing materials should be performed either before the converting operation actually starts, or else during this operation. Said materials could be added to the 20 other fractions of the charge or the slag formers, or entraining into the melt by pneumatic means.
The yield of cobalt in the slag can be optimized by adjusting the amount of oxidizing gas during the converting operations. This allows for the recovery of more than 90% by weight of the cobalt 25 présent in the cobalt-bearing materials.
The process is particularly suitable for the recovery of cobalt from cobalt-bearing materials comprising secondary batteries, spent batteries, or their scrap. The cobalt concentration that can reasonably be expected in the slag when working in preferred conditions amount to 30 between 2% and 20% by weight. The term battery scrap includes shredded batteries, selected battery fractions after e.g. shredding, and roasted batteries.
In a further embodiment, process steps are included for the recovery of cobalt and copper from the slag. This recovery may involve acidic aqueous leaching operation(s) or a step of reducing 35 smelting.
It should be noted that the smelting step with the production of copper or copper-nickel matte, or an impure alloy, and the converting step with the production of a crude métal from copper or copper-nickel matte, or an impure alloy, can be performed either in separate equipment, or else consecutively in the same equipment When using the same equipment, it is assumed that the 5 slag from the smelting step is tapped before initiating the converting step. According to the invention, cobalt-bearing batteries are then fed in the converting step. Furthermore, the optional step of recovering the copper and cobalt involving a deep reducing step, as explained in the second option below, may again be performed using the same equipment.
There are several known options for the recovery of cobalt and copper from the converter slag. A first option is a hydrometallurgy treatment, wherein the slag is leached or dissolved. The different metals, where under residual copper and cobalt are then recovered according to known processes such as filtration, précipitation and solvent extraction. Aim of such a hydrometallurgical dissolution step is to selectively recover valuable metals like copper and 15 cobalt; any co-dissolution of iron and alumina however would hâve a négative influence on the économie performance of the process, because of the increased consumption of reagents (both for the dissolution and the downstream removal) and the low value of these metallic impurities.
Several hydrometallurgical processes for the dissolution of cobalt and copper from said slags 20 are described in literature. Deng (Waste Manag. Res. 2007 Oct; 25(5):440-81 ) reports the dissolution of not only cobalt and copper, but also iron from a slag that has first been roasted with sulfuric acid. In the suggested flowsheet, iron is valorized as ferrous sulfate (after crystallization). A similar dissolution process is proposed by Buluth (Waste Manag. Res. 2006 Apr; 24(2):118-242). His work shows that a normal sulfuric acid leaching process gives slightly 25 higher dissolution yields for copper and cobalt than water leaching of the same slag after sulfuric acid roasting at 200°C. Sukla (Hydrometallurgy, Volume 16, Issue 2, dune 1986, Pages 153-165) also describes the water washing of slags that were roasted with either sulfuric acid or ammonium sulfate, and reports leach yields for both copper, cobalt and iron that are ail above 90%.
In order to eliminate both the expensive roasting step and the dissolution of iron, several processes are reported that use oxidative leaching in an autoclave. Anand (Hydrometallurgy, Volume 10, Issue 3, dune 1983, Pages 305-312) describes a process which is operated under pressure using dilute sulfuric acid and shows that even at high cobalt and copper yields, the co35 dissolution of iron can be avoided. Perederiy (“Dissolution of Valuable Metals from Nickel
Smelter Slags by Means of High Pressure Oxidative Acid Leaching”, PhD thesis by llya
Perederiy, University of Toronto, 2011) cornes to similar conclusions and demonstrates that at sufficiently high température and oxygen pressure, iron can be precipitated as crystalline hématite while cobalt and copper dissolves.
A second option is by pyro-metallurgy. A separate slag cleaning process is applied, exposing the slag to deep réduction, e.g. using an arc fumace under addition of carbon. Such a process is described in “Recovery of cobalt from slag in a DC arc fumace at Chambishi, Zambia”, RT Jones et al., Copper Cobalt Nickel and Zinc Recovery conférence, Victoria Falls, Zimbabwe, 1618 July 2001. Another process for slag cleaning under very reducing conditions is described in
WO 2016/023778. .
Table 1: Reference charge on smelter, without cobalt-bearing materials (comparative Example 1)
| Smelter | ||||||||||
| Input | Feed rate (t/h) | Composition (%) | ||||||||
| S | Cu | Ni | Fe | Co | Mn | Al | Si | Li | ||
| (FeO) | (CoO) | (MnO) | (AI2O3) | (SiO2) | (Li2O) | |||||
| Charge | 100 | 18 | 25 | 0,6 | 20 | - | - | - | - | - |
| 1 | 15 | - | ||||||||
| Flux | 20 | - | - | - | - | - | - | - | 100 | - |
| Output | ||||||||||
| Malte | 40 | 25 | 60 | 1,35 | 10,0 | - | - | - | - | - |
| Slag | 88,5 | - | 1,13 | 0,1 | - | - | - | - | - | |
| - | 23,2 | - | - | 1,13 | 39,5 | - |
| Converter | ||||||||||
| Input | Feed rate (t/h) | Composition (%) | ||||||||
| S | Cu | Ni | Fe | Co | Mn | Al | Si | Li | ||
| (FeO) | (CoO) | (MnO) | (AI2O3) | (SiO2) | (Li2O) | |||||
| Malte | 40 | 25 | 60 | 1,35 | 10 | - | - | - | - | - |
| Flux | 2,5 | - | - | - | - | - | - | - | 100 | - |
| Output | ||||||||||
| Blister | 24,0 | - | 98 | 2 | - | - | - | - | - | - |
| Slag | 10 | - | 4,8 | 0,6 | - | - | - | - | - | - |
| - | 51,5 | - | - | - | 25 | - |
This comparative Example 1 illustrâtes operating conditions for smelter and converter equipment working in tandem to treat typical copper-iron sulfidic ores. The matte produced in the smelter is fed to the converter. No batteries are added in this Example. The smelter is operated at a mean température of about 1175 °C.
The converter slag still contains a substantial amount of copper and will typically be recycled to the smelter. Alumina is suitably low in the smelter slag, and insignificant in the converter slag.
The smelter slag is clean and suitable for re-use. The converter is operated at a mean température of about 1300 °C.
Table 2: Reference charge with cobalt-bearing materials on smelter (comparative Example 2)
| Smelter | ||||||||||
| Input | Feed rate (t/h) | Composition (%) | ||||||||
| S | Cu | Ni | Fe | Co | Mn | Al | Si | Li | ||
| (FeO) | (CoO) | (MnO) | (AI2O3) | (SiO2) | (Li2O) | |||||
| Charge , | 100 | 18 | 25 | 0,6 | 20 | - | - | - | - | - |
| 1 | 15 | - | ||||||||
| Flux | 25 | - | - | - | - | - | - | - | 100 | - |
| Batteries | 20 | - | 10 | 4 | 14 | 10 | 2 | 12 | 0 | - |
| - | - | - | 4,1 | |||||||
| Output | ||||||||||
| Matte | 43,76 | 25 | 59,2 | 2,88 | 10,4 | 0,91 | - | - | - | - |
| Slag | 104,3 | - | 1,04 | 0,13 | - | 2,05 | - | - | - | - |
| - | 22,5 | 0,495 | 5,31 | 38,4 | 0,786 |
| Converter | ||||||||||
| Input | Feed rate (t/h) | Composition (%) | ||||||||
| S | Cu | Ni | Fe | Co | Mn | Al | Si | Li | ||
| (FeO) | (CoO) | (MnO) | (AI2O3) | (SIO2) | (Li2O) | |||||
| Matte | 43,76 | 25 | 59,2 3 | 2,88 | 10,4 | 0,91 | - | - | - | - |
| Flux | 2,9 | - | - | - | - | - | - | - | 100 | - |
| Output | ||||||||||
| Blister | 26,6 | - | 95,4 | 4,64 | - | - | - | - | - | - |
| Slag | 11,36 | - | 4,56 | 0,22 | - | - | - | - | - | - |
| - | 51,6 | 4,48 | - | - | 25,5 | - |
This comparative Example 2 illustrâtes typical working conditions for the smelter and converter 10 equipment treating copper-iron sulfidic ores similar to comparative Example 1, with however the différence that cobalt-bearing lithium-ion secondary batteries are fed to the smelter. The matte produced in the smelter is fed to the converter. The operating températures are according to Example 1.
Alumina in the smelter slag amounts to more than 5%, a figure indicating that the amount of batteries in the feed is against its upper bound.
Cobalt thus gets diluted in the smelter slag and in the converter slag, in concentrations 5 rendering recovery particularly arduous and expensive.
Table 3: Reference charge with cobalt-bearing materials on converter (Example according to the invention)
| Smelter | ||||||||||
| Input | Feed Rate (t/h) | Composition (%) | ||||||||
| S | Cu | Ni | Fe | Co | Mn | Al | Si | Li | ||
| (FeO) | (CoO) | (MnO) | (AI2O3) | (SIO2) | (LI2O) | |||||
| Charge | 100 | 18 | 25 | 0,6 | 20 | - | - | - | - | - |
| 1 | 15 | - | ||||||||
| Flux | 20 | - | - | - | - | - | - | - | 100 | - |
| Output | ||||||||||
| Matte | 40 | 25 | 60 | 1,35 | 10,0 | - | - | - | - | - |
| Slag | 88,5 | - | 1,13 | 0,1 | - | - | - | - | - | |
| - | 23,3 | - | - | 1,13 | 39,5 | - |
| Converter | ||||||||||
| Input | Feed Rate (t/h) | Composition (%) | ||||||||
| S | Cu | Ni | Fe | Co | Mn | Al | Si | Li | ||
| (FeO) | (CoO) | (MnO) | (AI2O3) | (SiO2) | (Li2O) | |||||
| Matte | 40 | 25 | 60 | 1,35 | 10 | - | - | - | - | - |
| Flux | 4,3 | - | - | - | - | - | - | - | 100 | - |
| Batteries | 20 | - | 10 | 4 | 14 | 10 | 2 | 12 | 0 | - |
| - | - | - | 4,1 | |||||||
| Output | ||||||||||
| Blister | 26,2 | - | 95,1 | 4,9 | - | - | - | - | - | - |
| Slag | 28,9 | - | 3,60 | 0,19 | - | - | - | - | - | - |
| - | 30,2 | 8,79 | 1,78 | 15,7 | 14,9 | 2,83 |
This Example according to the invention illustrâtes typical working conditions for the smelter and converter equipment treating copper-iron sulfidic ores similar to comparative Examples 1 and 2, with however the différence that cobalt-bearing lithium-ion secondary batteries are fed to the converter instead of to the smelter. The matte produced in the smelter is also fed to the converter. The operating températures are according to Examples 1 and 2.
Alumina is suitably low in the smelter slag, but amounts to 15.7% in the converter slag. As 5 explained above, such a high alumina concentration is acceptable in view ofthe conditions prevailing in a converter.
The smelter slag contains no cobalt, the cobalt being now concentrated in a low amount of converter slag. It is suitable for ecological re-use. The économie recovery of cobalt from the 10 converter slag is rendered possible.
Claims (7)
1. Process for the recovery of cobalt from cobalt-bearing materials, comprising the steps of:
- providing a converter furnace;
- charging slag formers and one or more of copper matte, copper-nickel matte, and impure alloy into the furnace, and injecting an oxidizing gas so as to smelt the charge in oxidizing conditions, thereby obtaining a molten bath comprising a crude métal phase, and a cobalt-bearing slag;
and,
- separating the crude métal phase from the cobalt-bearing slag;
characterized in that the cobalt-bearing materials are charged into the furnace.
2. Process according to claim 1, characterized in that more than 90% by weight of the cobalt présent in the cobalt-bearing materials is recovered in the cobalt-bearing slag, by adjusting the amount of oxidizing gas.
3. Process for the recovery of cobalt from cobalt-bearing materials according to claims 1 or 2, characterized in that the cobalt-bearing materials comprise secondary batteries, spent batteries, or their scrap.
4. Process for the recovery of cobalt from cobalt-bearing materials according to claim 3, characterized in that the cobalt in the slag amounting to between 2% and 20% by weight.
5. Process for the recovery of cobalt from cobalt-bearing materials according to any one of claims 1 to 4, further comprising steps for the recovery of cobalt and copper from the slag.
6. Process for the recovery of cobalt from cobalt-bearing materials according to claim 5, characterized in that the said steps for the recovery of cobalt and copper from the slag comprise an acidic aqueous leaching operation.
7. Process for the recovery of cobalt from cobalt-bearing materials according to claim 5, characterized in that the said steps for the recovery of cobalt and copper from the slag comprise a reducing smelting operation.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16195075.3 | 2016-10-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA19474A true OA19474A (en) | 2020-10-23 |
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