CN104805310B - Method for leaching cobalt from high-valence cobalt oxide-containing raw material - Google Patents
Method for leaching cobalt from high-valence cobalt oxide-containing raw material Download PDFInfo
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- CN104805310B CN104805310B CN201510185497.3A CN201510185497A CN104805310B CN 104805310 B CN104805310 B CN 104805310B CN 201510185497 A CN201510185497 A CN 201510185497A CN 104805310 B CN104805310 B CN 104805310B
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- raw material
- leaching
- high price
- cobalt oxide
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000010941 cobalt Substances 0.000 title claims abstract description 146
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000002386 leaching Methods 0.000 title claims abstract description 48
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 47
- 239000002994 raw material Substances 0.000 title claims abstract description 42
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 28
- 239000001117 sulphuric acid Substances 0.000 claims description 27
- 230000005070 ripening Effects 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003610 charcoal Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 239000002817 coal dust Substances 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 cobalt oxide Compound Chemical class 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000003245 coal Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 238000004537 pulping Methods 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 128
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 20
- 235000010755 mineral Nutrition 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 235000010269 sulphur dioxide Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- FWZLXRFUDMNGDF-UHFFFAOYSA-N [Co].[Cu]=O Chemical compound [Co].[Cu]=O FWZLXRFUDMNGDF-UHFFFAOYSA-N 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910001710 laterite Inorganic materials 0.000 description 2
- 239000011504 laterite Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- CRTGSPPMTACQBL-UHFFFAOYSA-N 2,3-dihydroxycyclopent-2-en-1-one Chemical compound OC1=C(O)C(=O)CC1 CRTGSPPMTACQBL-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- GHVNNFKGRJGVLD-UHFFFAOYSA-N cobalt;oxalic acid Chemical compound [Co].OC(=O)C(O)=O GHVNNFKGRJGVLD-UHFFFAOYSA-N 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910001655 manganese mineral Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for leaching cobalt from a high-valence cobalt oxide-containing raw material comprises the steps of crushing and finely grinding the high-valence cobalt oxide-containing raw material to be less than or equal to 0.25mm, uniformly mixing the crushed and finely ground high-valence cobalt oxide-containing raw material with a carbonaceous reducing agent such as coal powder, coke powder or carbon powder, controlling the water content in the mixture to be less than 20%, uniformly mixing the mixture with a certain amount of concentrated sulfuric acid under the condition of no water addition to obtain a mixture, curing the mixture at the temperature of 100-300 ℃, pulping and leaching the cured mixture with water, finally performing solid-liquid separation to obtain a cobalt-containing leachate, and obtaining a cobalt product from the cobalt-containing leachate through. The method adopts cheap and easily available carbonaceous reducing agent for reduction at low temperature, and has the advantages of simple process and equipment, low energy consumption, high cobalt leaching rate and low production cost.
Description
Technical field
The invention belongs to cobalt mineralss field of smelting, particularly relate to one and utilize carbonaceous reductant under cryogenic by sulphation also
Former ripening is from containing the method for leaching cobalt high price cobalt/cobalt oxide raw material.
Background technology
Cobalt has excellent physics, chemical property, is the important of high temperature alloy, magnetic material, chemical industry etc.
Raw material.The cobalt mineralss having been found that in nature have over one hundred kind, and industrial cobalt-containing ore is divided into sulphide ore and the big class of oxide ore two, sulfur
Change cobalt ore and typically produce various cobalt product by pyrometallurgical smelting, and cobalt oxide ore is cobalt/cobalt oxide at high price due to cobalt, as earthy cobalt,
Heterogenite, in addition to using pyrometallurgical smelting cobalt alloy, generally uses 2-cyclopenten-2,3-diol-1-one. soaking technology to process.Reclaim except smelting from cobalt ore
Outside cobalt, cobalt usually with other metallic ore association, such as association in nickel minerals, zinc ore, pyrite, in associated minerals, the recovery of cobalt becomes
The important sources that cobalt produces, and in the smelting of associated minerals, the many by-product form outputs with cobalt slag of cobalt, such as cobalt slag, then lead to
Cross reducing leaching mode from cobalt slag, extract cobalt.
Either cobalt oxide ore, or the cobalt slag of various industrial process output, cobalt therein is all with cobaltic high price cobalt/cobalt oxide
Form exists, and from such containing wet underwater welding cobalt high price cobalt/cobalt oxide raw material, is all by adding various going back during Ore Leaching
Former dose the high price cobalt of trivalent is reduced into the low price cobalt of bivalence after leach.CN1043788C discloses the leaching of a kind of earthy cobalt
Method, uses iron concentrate or cobalt iron concentrate to leach as reducing agent；CN101781716B discloses a kind of normal from laterite
Pressure leaches the method carrying cobalt, utilizes sodium thiosulfate to leach the cobalt in laterite as reducing agent；CN102358916A discloses one
Plant the hydrometallurgical extraction method reclaiming copper cobalt from cobalt copper oxide, cobalt copper oxide be finely ground to-200 mesh and account for 60%-90%,
Sulfur dioxide is used to carry out reduction acidleach as reducing agent；CN101792855A discloses one and separates from earthy cobalt and prepare Gao Song
The ratio method of high-purity oxalic acid cobalt, uses sodium sulfite to make reducing agent and leaches recovery manganese from earthy cobalt；CN101994003A discloses
A kind of selective extraction copper and technique of cobalt from heterogenite, uses sulphuric acid and sodium sulfite reducing leaching cobalt；CN103789543A
Disclose a kind of cobalt sulfide and mix the method leached with heterogenite, first mix leaching with heterogenite with cobalt sulfide concentrate, add the most again
Enter sodium sulfite or sodium pyrosulfite or sulfur dioxide is made reducing agent and continued to leach remaining heterogenite；CN101898802A discloses
A kind of method extracting cobalt production cobaltous chloride from low-grade cobalt residue, the cobalt slag produced except cobalt process for oxydrolysis precipitation, with Asia
Sodium sulfate or hydrogen peroxide are that reducing agent carries out reduction acid leaching extraction cobalt.
Due to containing the conventional wet smelting process of high price cobalt/cobalt oxide raw material be required for adding substantial amounts of sodium sulfite, sulfur dioxide,
Reducing agent made by hydrogen peroxide etc., and reducing agent consumes big and price is high, causes production cost high, and reducing agent source inconvenience.CN
103882226A disclose a kind of economy and cleaning easy from the method containing high price cobalt/cobalt oxide leaching cobalt, utilize simple substance charcoal to go back
Former dose, sulphuric acid carry out reducing leaching as leaching agent, utilize charcoal cheap, that be easy to get to replace the reducing agents such as sulfur dioxide, reduce life
Produce cost, simplify flow process, but this method is first will to contain high price cobalt/cobalt oxide water to be modulated into cobalt oxide ore mass concentration 20%～50%
Ore pulp, then by 150～500kg/t butt ore deposits add concentrated sulphuric acids leach, react due under acidic aqueous solution, ore deposit
Sulfuric acid concentration in slurry is low, the redox reaction poor activity of charcoal and sulphuric acid, the charcoal amount of interpolation need account for ore quality 20% with
On can be only achieved the effect of cobalt leaching rate 88%, charcoal is incorporated as the 20 of the required charcoal theoretical amount of the reduction such as cobalt in cobalt raw material, manganese, ferrum
More than Bei, cause a large amount of charcoal consumption excessive, relatively costly, and the remaining a large amount of unreacted charcoals of leached mud, slag needs further
Process, complex process.
Summary of the invention
It is an object of the invention to for problem present in the high price existing wet treatment method of cobalt/cobalt oxide raw material, it is desirable to provide one
Planting the both economically and environmentally beneficial low temperature self-heating reduction maturation process method containing high price cobalt/cobalt oxide raw material, concrete grammar is containing high price cobalt
Oxide raw material is mixed homogeneously with the carbonaceous reductant such as coal dust, coke powder, powdered carbon after crushing fine grinding, control aqueous in compound≤20%,
Be subsequently adding concentrated sulphuric acid mix uniformly after carry out self-heating ripening, the trivalent cobalt in raw material is reduced to bivalence cobalt, then uses water slurry
Leach the cobalt in ripening material.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, its principle is the strong oxidizing property utilizing concentrated sulphuric acid, heat
Concentrated sulphuric acid be reduced into sulfur dioxide by carbonaceous reductants such as coal dusts, in the sulfur dioxide direct-reduction cobalt/cobalt oxide that reduction generates
Trivalent cobalt is bivalence cobalt, forms cobaltous sulfate soluble in water, thus realizes by reduction-oxidation cobalt under carbonaceous reductant low temperature, this mistake
In journey, sulphuric acid is the acidulant of leaching cobalt, is again the catalytic action promoting low temperature charcoal reduction high price cobalt.
C+2H2SO4(dense)=CO2↑+2SO2+2H2O
SO2+Co2O3+H2SO4=2CoSO4+H2O
Overall reaction:
C+2Co2O3+4H2SO4(dense)=4CoSO4+CO2↑+4H2O
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, is containing the cobalt containing high price cobalt/cobalt oxide when processing raw material
During soil ore deposit, the manganese oxide mineral in earthy cobalt also can be reduced to bivalent manganese by carbonaceous reductant, thus the mineral structure of earthy cobalt,
Make the cobalt mineralss being wrapped in manganese mineral matrix dissociate, thus improve the leaching rate of cobalt.
C+2H2SO4(dense)=CO2↑+2SO2+2H2O
SO2+MnO2=MnSO4
Overall reaction:
C+2MnO2+2H2SO4(dense)=2MnSO4+CO2↑+2H2O
The present invention is achieved through the following technical solutions.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt, it is characterised in that comprise the following steps:
(1) join ore deposit: by crushing, be finely ground to≤0.25mm containing high price cobalt/cobalt oxide raw material powder, reduce with a certain amount of carbonaceous
Agent mix homogeneously, described carbonaceous reductant is one or more the mixture in coal dust, coke powder, powdered carbon.
(2) reduction ripening: the compound of step (1) gained is mixed thoroughly with a certain amount of concentrated sulphuric acid in the case of not adding water
To mix, then ripening under 100～300 DEG C of temperature conditionss, the curing time 0.5～4h.
(3) leach: by the material after step (2) reduction ripening, the pulp that adds water leaches, and extraction temperature 30～95 DEG C, during leaching
Between 10～120min.
(4) solid-liquid separation: leach after terminating, ore pulp carries out solid-liquid separation through dense or filtration, obtains cobalt-bearing leaching solution and leaching
Slag, cobalt-bearing leaching solution obtains cobalt product by common process.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, it is characterised in that join ore deposit described in step (1), be
High price cobalt/cobalt oxide raw material will be contained crush, be finely ground to≤0.15mm, and then mix homogeneously with a certain amount of carbonaceous reductant, control
In compound aqueous≤20%.
The present invention unless otherwise indicated beyond, ratio, percentage ratio, concentration are all on the basis of quality.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, it is characterised in that the described a certain amount of charcoal of step (1)
Matter reducing agent, refers to that reducing agent addition is containing required theoretical consumption charcoal amounts of reduction such as cobalt, manganese, ferrum in high price cobalt/cobalt oxide raw material
1～2 times of addition, the preferred coal dust of reducing agent.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, it is characterised in that step (2) is described a certain amount of dense
Sulphuric acid, refers to that the addition of concentrated sulphuric acid is 1～2 times containing high price cobalt/cobalt oxide raw material theory acid consumption, preferably 1～1.5 times, institute
State the sulphuric acid that concentrated sulphuric acid is concentration >=90%.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, it is characterised in that the mix described in step (2),
Sulphuric acid initial concentration >=75% after mix.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, it is characterised in that the reduction ripening described in step (2),
It is to utilize reaction self-heating to complete, curing temperature 150～250 DEG C, the curing time 0.5～2h.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, it is characterised in that the leaching described in step (3), leaching
Go out temperature 30～60 DEG C, extraction time 10～30min.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, it is characterised in that the described cobalt/cobalt oxide containing high price is former
Material is one or more the mixture in earthy cobalt, heterogenite, copper-cobalt oxidation ore, cobalt slag.
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt of the present invention, is the strong oxidizing property utilizing concentrated sulphuric acid, the dense sulfur of heat
Acid is reduced into sulfur dioxide by carbonaceous reductants such as coal dusts, and the sulfur dioxide direct-reduction that reduction generates is containing high price cobalt/cobalt oxide raw material
In cobalt, ferrum, manganese etc., thus realize with reduction under carbonaceous reductant low temperature containing high price cobalt/cobalt oxide raw material, then pass through water logging
Extract cobalt.The method has the advantage that raw material sources are wide and cheap, and technical process and equipment are simple, stable operation,
Energy consumption is low, and cobalt leaching rate is high, and production cost is low, has wide applicability, significant economic benefit and social benefit.
Accompanying drawing explanation
Accompanying drawing is the principle process chart of the inventive method.
Detailed description of the invention
A kind of method containing high price cobalt/cobalt oxide raw material leaching cobalt, be the cobalt/cobalt oxide raw material containing high price is crushed, is finely ground to≤
After 0.25mm, mix homogeneously with the carbonaceous reductant such as coal dust, coke powder or powdered carbon, control aqueous in compound to be less than 20%, then
Mix thoroughly with a certain amount of concentrated sulphuric acid in the case of not adding water and obtain mix, then ripening under 100～300 DEG C of temperature conditionss,
The material that ripening is good leaches by water slurryization again, and last solid-liquid separation obtains the leachate containing cobalt, and cobalt-bearing leaching solution is obtained by common process
To cobalt product.
With nonlimiting examples, the method for the present invention is further described below, with contribute to understanding present disclosure and
Its advantage, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Embodiment 1
Take 100g and be finely ground to 0.15mm containing cobalt 4.5%, earthy cobalt containing manganese 3.4%, iron content 5.9%, by cobalt in earthy cobalt, manganese,
1.5 times of the required theoretical consumption charcoal amount of the reduction such as ferrum, add the brown coal powder mix homogeneously that fixed carbon content is 70% and obtain aqueous 5%
Compound, then toward compound adds 98% sulphuric acid of 1.1 times of theoretical acids consumptions, after mixing thoroughly at a temperature of 250 DEG C ripening 2 hours,
The ripening material obtained 90 DEG C, go out 1h with water logging under the conditions of liquid-solid ratio 4:1, be filtrated to get cobalt sulfate solution and leached mud, cobalt
Leaching rate 99.5%.
Embodiment 2
Take 100kg and be finely ground to 0.15mm containing cobalt 4.5%, earthy cobalt containing manganese 3.4%, iron content 5.9%, by cobalt in earthy cobalt, manganese,
1.5 times of the required theoretical consumption charcoal amount of the reduction such as ferrum, add the anchracite duff mix homogeneously that fixed carbon content is 75% and obtain aqueous 10%
Compound, then toward compound adds 90% sulphuric acid of 1 times of theoretical acid consumption, the sulphuric acid initial concentration 80% after mix, so
After utilize reaction heat self-heating to be warmed up to 160 DEG C of ripenings 2 hours, the ripening material obtained 30 DEG C, use water under the conditions of liquid-solid ratio 4:1
Leach 0.5h, be filtrated to get cobalt sulfate solution and leached mud, the leaching rate 96.2% of cobalt.
Embodiment 3
Take 100g to contain cobalt 6.5%, be finely ground to 0.15mm containing manganese 1.4%, iron content 5.4%, the heterogenite of cupric 7.5%, by water cobalt
In ore deposit, required theoretical consume charcoal amount 1.5 times of the reduction such as cobalt, manganese, ferrum, add the brown coal powder mix homogeneously that fixed carbon content is 70%
Obtain the compound of aqueous 5%, then in compound, add 93% sulphuric acid that 1.2 times of theoretical acids consume, 150 DEG C of temperature after mixing thoroughly
The lower ripening of degree 2 hours, the ripening material obtained 90 DEG C, go out 1h with water logging under the conditions of liquid-solid ratio 4:1, be filtrated to get cobaltous sulfate molten
Liquid and leached mud, the leaching rate 97.5% of cobalt.
Embodiment 4
Take the cobalt slag containing cobalt 5.5% of 100g nickel wet method refining fusion process oxidation precipitation output, required theoretical by reduction such as cobalts in cobalt slag
1.2 times of consumption charcoal amount, add the brown coal powder mix homogeneously that fixed carbon content is 70% and obtain the compound of aqueous 15%, the most past
Compound adds 93% sulphuric acid of 1.2 times of theoretical acids consumption, after mixing thoroughly at a temperature of 150 DEG C ripening 2 hours, the ripening material obtained
50 DEG C, go out 1h with water logging under the conditions of liquid-solid ratio 4:1, be filtrated to get cobalt sulfate solution and leached mud, the leaching rate 98% of cobalt.
Claims (9)
1. the method containing high price cobalt/cobalt oxide raw material leaching cobalt, it is characterised in that comprise the following steps:
(1) join ore deposit: by crushing, be finely ground to≤0.25mm containing high price cobalt/cobalt oxide raw material powder, reduce with a certain amount of carbonaceous
Agent mix homogeneously, described carbonaceous reductant is one or more the mixture in coal dust, coke powder, powdered carbon；
(2) reduction ripening: the compound of step (1) gained is mixed thoroughly with a certain amount of concentrated sulphuric acid in the case of not adding water
To mix, then ripening under 100～300 DEG C of temperature conditionss, the curing time 0.5～4h；
(3) leach: by the material after step (2) reduction ripening, the pulp that adds water leaches, and extraction temperature 30～95 DEG C, during leaching
Between 10～120min；
(4) solid-liquid separation: leach after terminating, ore pulp carries out solid-liquid separation through dense or filtration, obtains cobalt-bearing leaching solution and leaching
Slag, cobalt-bearing leaching solution obtains cobalt product by common process.
Method the most according to claim 1, it is characterised in that join ore deposit described in step (1), is will be containing high price cobalt oxide
Compound raw material crushes, is finely ground to≤0.15mm, then mixs homogeneously with a certain amount of carbonaceous reductant, controls in compound aqueous
≤ 20%.
Method the most according to claim 1, it is characterised in that the described a certain amount of carbonaceous reductant of step (1), be
Refer to that reducing agent addition is containing cobalt, manganese, 1～2 times of addition of the required theoretical consumption charcoal amount of ferrum reduction in high price cobalt/cobalt oxide raw material, also
Former dose is coal dust.
Method the most according to claim 1, it is characterised in that the described a certain amount of concentrated sulphuric acid of step (2), refers to dense
The addition of sulphuric acid is 1～2 times containing high price cobalt/cobalt oxide raw material theory acid consumption, and described concentrated sulphuric acid is the sulphuric acid of concentration >=90%.
Method the most according to claim 1, it is characterised in that the mix described in step (2), the sulphuric acid after mix
Initial concentration >=75%.
Method the most according to claim 1, it is characterised in that the reduction ripening described in step (2), is to utilize reaction
Self-heating completes, curing temperature 150～250 DEG C, the curing time 0.5～2h.
Method the most according to claim 1, it is characterised in that the leaching described in step (3), extraction temperature 30～60 DEG C,
Extraction time 10～30min.
Method the most according to claim 1, it is characterised in that the described cobalt/cobalt oxide raw material containing high price is earthy cobalt, water
One or more mixture in cobalt ore, copper-cobalt oxidation ore, cobalt slag.
Method the most according to claim 4, it is characterised in that the addition of step (2) concentrated sulphuric acid is for containing high price cobalt oxide
Compound raw material theory acid consumption 1～1.5 times.
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| CN105755282A (en) * | 2016-05-14 | 2016-07-13 | 北京矿冶研究总院 | Method for simultaneously treating submarine cobalt manganese oxide resources and multi-metal sulfides |
| CN109338122A (en) * | 2018-11-06 | 2019-02-15 | 广东佳纳能源科技有限公司 | A kind of leaching method of heterogenite |
| CN110983057B (en) * | 2019-12-04 | 2023-08-08 | 北京科技大学 | Soot treatment method capable of realizing UPOPs synthesis retardation and low-temperature decomposition |
| CN111961879A (en) * | 2020-08-20 | 2020-11-20 | 湖南中伟新能源科技有限公司 | Method for synergistically leaching cobalt sulfide and cobaltosic oxide, preparation method of nickel-cobalt-manganese ternary precursor and preparation method of cobalt |
| CN112760480B (en) * | 2020-12-22 | 2023-01-13 | 衢州华友钴新材料有限公司 | Method for improving oxygen pressure leaching efficiency of copper sulfide cobalt concentrate |
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