CN102021325B - Method for respectively leaching copper and cobalt from copper and cobalt concentrate - Google Patents
Method for respectively leaching copper and cobalt from copper and cobalt concentrate Download PDFInfo
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- CN102021325B CN102021325B CN2010105899063A CN201010589906A CN102021325B CN 102021325 B CN102021325 B CN 102021325B CN 2010105899063 A CN2010105899063 A CN 2010105899063A CN 201010589906 A CN201010589906 A CN 201010589906A CN 102021325 B CN102021325 B CN 102021325B
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- copper
- cobalt
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- concentrate
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- 239000010949 copper Substances 0.000 title claims abstract description 148
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 121
- 239000010941 cobalt Substances 0.000 title claims abstract description 103
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 103
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000012141 concentrate Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002386 leaching Methods 0.000 title abstract description 72
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 42
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 65
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 17
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- -1 iron ion Chemical class 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 abstract description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 239000001099 ammonium carbonate Substances 0.000 abstract 2
- 239000000706 filtrate Substances 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 abstract 1
- 235000010265 sodium sulphite Nutrition 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000008399 tap water Substances 0.000 description 17
- 235000020679 tap water Nutrition 0.000 description 17
- 239000002893 slag Substances 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000438 diphosphorus tetroxide Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical group [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 206010067171 Regurgitation Diseases 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for respectively leaching copper and cobalt from a copper and cobalt concentrate. The method comprises the following steps of: (1) ammonia leaching: adding the copper and cobalt concentrate into bottom water, adding ammonium carbonate according to a molar ratio that the ammonium carbonate to the copper element in the copper and cobalt concentrate is 1:4-12, introducing ammonia gas or ammonia water according to the molar ratio that the ammonia gas or the ammonia water to the copper element is 1:4-12, adding sodium chlorate in an amount which is 0.3 to 0.5 times the mass of the copper element, reacting at the temperature of between 30 and 60 DEG C for 1 to 3 hours, and filtering to obtain filtrate and filter residues respectively; and (2) acid leaching: adding the filter residues into the bottom water, adding sulfuric acid or hydrochloric acid to regulate the pH value to be between 0.5 and 1.5, adding sodium sulfite in an amount which is 1.2 to 1.5 times the total mass of the copper element and the cobalt element in the filter residues, reacting at the temperature of between 60 and 80 DEG C for 1 to 3 hours, and filtering to obtain filter residues and filtrate respectively. In the method, copper can be selectively leached, while the cobalt is not leached in the step of ammonia leaching; and the cobalt and the residual copper can be completely leached in the step of acid leaching.
Description
Technical field
The present invention relates to chemical field, relate in particular to a kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively.
Background technology
Whole world cobalt resource is rare, and cobalt metal is important strategic material.China cobalt resource overwhelming majority is an associated resources, like linnaeite, copper cobalt ore and nickel cobalt ore etc.Wherein, the copper cobalt ore is the important source of cobalt.The copper cobalt ore is main with copper, and cobalt is mixture and is present in the copper cobalt ore.Therefore, the separation of copper cobalt has just become to make full use of one of subject matter of cobalt resource.
The copper cobalt ore needs to remove impurity through floatation process earlier usually, obtains the copper cobalt concentrate.Copper mainly is to exist with the cupric oxide form in the copper cobalt concentrate, add a spot of cupric sulfide and cuprous sulfide, and cobalt mainly is to exist with the cobaltous sulfide form, contains the cobalt that the small amounts form exists.
Conventional leaching copper and the treatment process of cobalt have after pressure oxidation leaching and the sulfurization roasting direct acidleach etc.But in these methods, metals such as cobalt, copper, iron and manganese are leached usually together, and typical leach liquor content is behind readjustment pH3.5～4.0 deironing and the aluminium: Co:18～23g/L, Cu:16～21g/L, Fe:100～800mg/L, Mn:1～7g/L.Because wherein the content of metallic copper and cobalt is roughly suitable, so come very difficulty of extracting and separating copper and cobalt, need add one specially and drag for copper cash elder generation extracting copper with common P204, handle the low copper feed liquid of high cobalt with P204 again.And iron ion and 1～7g/L mn ion that 100～800mg/L is arranged in advancing to drag for the removal of impurities liquid of copper extraction section; Part iron ion and mn ion possibly get in the copper electrodeposition rich solution through mixed phase, carry secretly etc.; Anode lead and stainless steel cathode there are heavy corrosion, the anode sheet are peeled off, the plate buckling short circuit; The negative plate face produces fine and close aperture, and negative electrode goes out groove, peels off difficulty.
In addition, because the taste of the cobalt resource of China is lower, the recovery of cobalt metal and associated metal thereof is low and production cost is high.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively, can be in different steps selective leaching copper and cobalt, and the leaching yield of copper and cobalt is high.
The invention provides a kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively, may further comprise the steps:
(1) ammonia soaks: get the copper cobalt concentrate; Ratio in solid-to-liquid ratio 1: 2～6 is put in the end water, and in the copper cobalt concentrate in the mol ratio of copper be that 1: 4～12 ratio adds volatile salt, and be that 1: 4～12 ratio feeds ammonia or ammoniacal liquor in mol ratio with copper; Extraordinarily go into VAL-DROP by 0.3～0.5 of copper quality subsequently; Under 30～60 ℃ temperature, reacted 1～3 hour, and filtered, get filtrating and filter residue respectively;
(2) acidleach: get filter residue; Ratio in solid-to-liquid ratio 1: 2～6 is put in the end water; Adding sulfuric acid or salt acid for adjusting pH value is 0.5～1.5, extraordinarily goes into S-WAT by 1.2～1.5 of copper in the filter residue and cobalt element total mass, under 60～80 ℃ temperature, reacts 1～3 hour; Filter, get filter residue and filtrating respectively.
It is raw material that the present invention gets the copper cobalt concentrate.Wherein, copper mainly is to exist with the cupric oxide form, add a spot of cupric sulfide and cuprous sulfide, and cobalt mainly is to exist with the cobaltous sulfide form, contains the cobalt that the small amounts form exists.
Can through treat mechanically the copper cobalt concentrate tentatively be pulverized earlier in the step (1), also available ball mill is further pulverized the copper cobalt concentrate.Preferably, copper cobalt concentrate mean particle size is 0.1～0.2mm, and granularity is crossed senior general and caused leaching not exclusively, and leaching yield reduces; Undersized, then grinding efficiency is low.
End water can be taken from tap water, slag washing water, drag for copper raffinate or other waste water etc.Preferably, this end water is tap water, take convenient and cost low.
Utilizing sal volatile, ammonia or ammoniacal liquor to make leaching agent, is to utilize copper to be easy to generated the extraction that cuprammonium complexing ion and then water-soluble this characteristic realize copper by ammonia dissolving.Add carbonate and be in order to form buffered soln with ammoniacal liquor, the pH value of keeping reaction system is about 10, prevents that pH value is too high and causes cupric ammine complex hydrolysis formation to precipitate.Simultaneously and since the complex ability of cobalt ion, iron ion and mn ion and ammonia very a little less than, so leached hardly.It is not enough that free ammonia is crossed that I haven't seen you for ages and caused with the ammonia of cupric ion complexing, and then cause copper leaching rate low; Free ammonia is crossed the waste that can cause sal volatile, ammonia or ammoniacal liquor at most, and the volatilization that can increase the weight of ammonia, influences operating environment.Preferably, the mol ratio of the copper of copper cobalt concentrate, volatile salt and ammoniacal liquor is 1: 6～10: 6～10.More preferably, the mol ratio of the copper of copper cobalt concentrate, volatile salt and ammoniacal liquor is 1: 9: 9.Ammonia is soluble in solvent and forms ammoniacal liquor, so the usage quantity of ammonia is identical with ammoniacal liquor by mole number.The present invention adopts the normal pressure ammonia leaching process, need not to use autoclave.
Sal volatile, ammonia or ammoniacal liquor can recycles, are used for the process of extraction agent extracting coppers such as PT5050, LIX984N, and ammonia is arranged in its raffinate, can also add ammonia as end water and soak in the process.
Add the cupric sulfide of VAL-DROP in can the cupric oxide cobalt concentrate, and then improve the leaching yield of copper.Preferably, adding the amount of VAL-DROP and the mass ratio of copper is 1: 2.
The reaction equation that relates in the step (1) is following:
CuO+2NH
4OH+2NH
4 +→Cu(NH
3)
4 2++3H
2O
3CuS+6NH
3.H
2O+6NH
4 ++ClO
3 -→3Cu(NH
3)
4 2++3S+Cl
-+9H
2O
3CuS+4ClO
3 -+12NH
3.H
2O→3Cu(NH
3)
4 2++4Cl
-+3SO
4 2-+12H
2O
3Cu
2S+ClO
3 -+6NH
3.H
2O+6NH
4 +→3Cu(NH
3)
4 2++Cl
-+3CuS+9H
2O
Gained filtrating can be advanced copper extraction line in the step (1).Ammonia soaks in the process, because the complex ability of cobalt, iron and manganese and ammonia is low, so the leaching yield of these metals is very low, therefore can guarantee that foreign matter content is low in the copper electrolyte.Copper in the filtrating is about 7～15g/L, and cobalt contents is 0.05～0.4g/L, and iron level is 0.1～7mg/L, and the leaching yield of copper is 80%～99%, and the leaching yield of cobalt is 0.5%～3%, and iron, manganese leaching yield are 0.1%～0.5%.
Filter residue gets into acidleach in the step (2).
Step (2) acidleach process is mainly adding reductive agent S-WAT cobalt ion is reduced, and then leaches divalence cobalt and remaining little copper.Preferably, the mass ratio of copper and cobalt element total mass is 3: 2 in the amount of S-WAT and the filter residue.
End water can be taken from tap water, slag washing water, raffinate or other waste water etc.Preferably, this end water is tap water, take convenient and cost low.
The reaction equation that relates in the step (2) is following:
CoS+6H
++SO
3 2-→Co
2++3S+3H
2O
CoO+2H
+→Co
2++H
2O
Co
2O
3+4H
++SO
3 2-→2Co
2++2H
2O+SO
4 2-
2CuS+6H
++SO
3 2-→Cu
2++3S+3H
2O
Cu
2S+6H
++SO
3 2-→2Cu
2++2S+3H
2O
CuO+2H
+→Cu
2++H
2O
The gained filter residue is dried slag cobalt (cobalt mainly is to exist with sulfuration cobalt ore and partially oxidation cobalt ore) in the step (2).Dried slag cobalt contents is 0.08%～0.15%, and copper content is 0.08%～0.16%.The total leaching yield of cobalt is 98.8%～99.5%, and the total leaching yield of copper is 98.6%～99.0%.
Filtrating can advance to extract line.Preferably, filtrating is removed iron ion or aluminum ion through removal of impurities earlier before getting into the extraction line in the step (2).Copper content is low in this filtrating, and therefore, the rate of loss of copper is little in the removal of impurities process.
Remove iron ion process can for: in the filtrating of step (2), add ydrogen peroxide 50, VAL-DROP or bubbling air and become ferric iron to oxidation of divalent, remove ferric iron with yellow modumite method, pyrrhosiderite, rhombohedral iron ore etc. subsequently, get into the extraction line afterwards.
The method that from the copper cobalt concentrate, leaches copper and cobalt respectively provided by the invention has following beneficial effect;
(1) can be in different steps selective leaching copper and cobalt, ammonia soaks that process is alternative to be leached copper and do not leach cobalt, reduction acidleach process can leach cobalt and remaining copper fully, so the leaching yield of copper and cobalt height;
(2) to soak in the process in the copper leach liquor cobalt ion, iron ion and mn ion content low for ammonia, can guarantee that foreign matter content is low in the copper electrolyte;
(3) copper content is very low in the acidleach filtrating, and the rate of loss of copper is little in the removal of impurities process;
(4) equipment required for the present invention is simple, does not need stoving oven or autoclave, and ammonia and volatile salt can recycles, so production cost is lower, is applicable to industriallization.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Embodiment
The following stated is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also are regarded as protection scope of the present invention.Fig. 1 is a schematic flow sheet of the present invention.
Embodiment one
A kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively may further comprise the steps:
(1) ammonia soaks: the equal granularity of making even is that (Cu:6.88% Co:8.01%), puts in the 300mL tap water in 1: 3 ratio of solid-to-liquid ratio, according to the Cu of copper cobalt concentrate: (NH for the ball milling copper cobalt concentrate 100g of 0.12mm
4)
2CO
3: NH
3Mol ratio be to add volatile salt 58g, strong aqua 50mL at 1: 6: 6, add VAL-DROP 1.3g, reaction is 3 hours under 30 ℃ temperature, filters, and gets filtrating and filter residue respectively.Copper in the ammonia leaching liquid is 9.6g/L, and cobalt contents 0.3g/L, iron level are 5.5mg/L, and the leaching yield of copper is 87.5%, and the leaching yield of cobalt is 1.6%, and iron, manganese leaching yield are 0.05%, and filter residue is 87.1g.
(2) acidleach: get filter residue, put in the 350mL tap water in 1: 4 ratio of solid-to-liquid ratio, adding the sulphur acid for adjusting pH value is 1.0; Extraordinarily go into S-WAT 12.5g by 1.5 of copper in the filter residue and cobalt element total mass; Reaction is 1.5 hours under 60 ℃ temperature, filters, and gets filter residue and filtrating respectively.The dried slag cobalt contents of filter residue is 0.11%, and copper content is 0.16%.The total leaching yield of cobalt is 99.1%, and the total leaching yield of copper is 98.6%.
Embodiment two
A kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively may further comprise the steps:
(1) ammonia soaks: the equal granularity of making even is that (Cu:6.88% Co:8.01%), puts in the 300mL tap water in 1: 3 ratio of solid-to-liquid ratio, according to the Cu of copper cobalt concentrate: (NH for the ball milling copper cobalt concentrate 100g of 0.17mm
4)
2CO
3: NH
3Mol ratio be to add volatile salt 87g, strong aqua 75mL at 1: 9: 9, add VAL-DROP 1.3g, reaction is 3 hours under 30 ℃ temperature, filters, and gets filtrating and filter residue respectively.Copper in the ammonia leaching liquid is 12.5g/L, and cobalt contents 0.4g/L, iron level are 0.1mg/L, and the leaching yield of copper is 88.8%, and the leaching yield of cobalt is 2.6%, and iron, manganese leaching yield are 0.01%, and filter residue is 87.9g.
(2) acidleach: get filter residue, put in the 350mL tap water in 1: 4 ratio of solid-to-liquid ratio, adding the sulphur acid for adjusting pH value is 0.5; Extraordinarily go into S-WAT 9g by 1.5 of copper in the filter residue and cobalt element total mass; Reaction is 1.5 hours under 60 ℃ temperature, filters, and gets filter residue and filtrating respectively.The dried slag cobalt contents of filter residue is 0.10%, and copper content is 0.12%.The total leaching yield of cobalt is 99.3%, and the total leaching yield of copper is 98.9%.
Embodiment three
A kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively may further comprise the steps:
(1) ammonia soaks: the equal granularity of making even is that (Cu:6.88% Co:8.01%), puts in the 600mL tap water in 1: 6 ratio of solid-to-liquid ratio, according to the Cu of copper cobalt concentrate: (NH for the ball milling copper cobalt concentrate 100g of 0.10mm
4)
2CO
3: NH
3Mol ratio be to add volatile salt 87g, strong aqua 75mL at 1: 9: 9, add VAL-DROP 1.3g, reaction is 3 hours under 50 ℃ temperature, filters, and gets filtrating and filter residue respectively.Copper in the ammonia leaching liquid is 7.1g/L, and cobalt contents 0.2g/L, iron level are 4.0mg/L, and the leaching yield of copper is 85.3%, and the leaching yield of cobalt is 2.4%, and iron, manganese leaching yield are 0.2%, and filter residue is 88.7g.
(2) acidleach: get filter residue, put in the 270mL tap water in 1: 3 ratio of solid-to-liquid ratio, adding the sulphur acid for adjusting pH value is 1.0; Extraordinarily go into S-WAT 7.3g by 1.2 of copper in the filter residue and cobalt element total mass; Reaction is 2 hours under 60 ℃ temperature, filters, and gets filter residue and filtrating respectively.The dried slag cobalt contents of filter residue is 0.13%, and copper content is 0.13%.The total leaching yield of cobalt is 98.8%, and the total leaching yield of copper is 98.9%.
Embodiment four
A kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively may further comprise the steps:
(1) ammonia soaks: the equal granularity of making even is that (Cu:6.88% Co:8.01%), puts in the 300mL tap water in 1: 3 ratio of solid-to-liquid ratio, according to the Cu of copper cobalt concentrate: (NH for the ball milling copper cobalt concentrate 100g of 0.20mm
4)
2CO
3: NH
3Mol ratio be to add volatile salt 87g, strong aqua 75mL at 1: 9: 9, add VAL-DROP 1.3g, reaction is 3 hours under 50 ℃ temperature, filters, and gets filtrating and filter residue respectively.Copper in the ammonia leaching liquid is 11.32g/L, and cobalt contents 0.3g/L, iron level are 7mg/L, and the leaching yield of copper is 83.9%, and the leaching yield of cobalt is 2.1%, and iron, manganese leaching yield are 0.15%, and filter residue is 89.4g.
(2) acidleach: get filter residue, put in the 450mL tap water in 1: 5 ratio of solid-to-liquid ratio, adding the sulphur acid for adjusting pH value is 0.5; Extraordinarily go into S-WAT 11.1g by 1.5 of copper in the filter residue and cobalt element total mass; Reaction is 2 hours under 60 ℃ temperature, filters, and gets filter residue and filtrating respectively.The dried slag cobalt contents of filter residue is 0.09%, and copper content is 0.14%.The total leaching yield of cobalt is 99.4%, and the total leaching yield of copper is 98.7%.
Embodiment five
A kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively may further comprise the steps:
(1) ammonia soaks: the equal granularity of making even is that (Cu:6.88% Co:8.01%), puts in the 300mL tap water in 1: 3 ratio of solid-to-liquid ratio, according to the Cu of copper cobalt concentrate: (NH for the ball milling copper cobalt concentrate 100g of 0.20mm
4)
2CO
3: NH
3Mol ratio be to add volatile salt 116g, strong aqua 100mL at 1: 12: 12, add VAL-DROP 1.3g, reaction is 3 hours under 50 ℃ temperature, filters, and gets filtrating and filter residue respectively.Copper in the ammonia leaching liquid is 12.48g/L, and cobalt contents 0.4g/L, iron level are 0.1mg/L, and the leaching yield of copper is 88.7%, and the leaching yield of cobalt is 3%, and iron, manganese leaching yield are 0.01%, and filter residue is 87.9g.
(2) acidleach: get filter residue, put in the 450mL tap water in 1: 5 ratio of solid-to-liquid ratio, adding the sulphur acid for adjusting pH value is 0.5; Extraordinarily go into S-WAT 8.9g by 1.5 of copper in the filter residue and cobalt element total mass; Reaction is 2 hours under 60 ℃ temperature, filters, and gets filter residue and filtrating respectively.The dried slag cobalt contents of filter residue is 0.10%, and copper content is 0.10%.The total leaching yield of cobalt is 99.3%, and the total leaching yield of copper is 99.0%.
Embodiment six
A kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively may further comprise the steps:
(1) ammonia soaks: the equal granularity of making even is that (Cu:6.88% Co:8.01%), puts in the 200mL tap water in 1: 2 ratio of solid-to-liquid ratio, according to the Cu of copper cobalt concentrate: (NH for the ball milling copper cobalt concentrate 100g of 0.10mm
4)
2CO
3: NH
3Mol ratio be to add volatile salt 38g, strong aqua 33mL at 1: 4: 4, add VAL-DROP 2.1g, reaction is 2 hours under 40 ℃ temperature, filters, and gets filtrating and filter residue respectively.Copper in the ammonia leaching liquid is 17.5g/L, and cobalt contents 0.4g/L, iron level are 6.2mg/L, and the leaching yield of copper is 80.3%, cobalt leaching yield 1.4%, and iron, manganese leaching yield are 0.05%, filter residue is 91.1g.
(2) acidleach: get filter residue, put in the 182mL slag washing water in 1: 2 ratio of solid-to-liquid ratio, adding the sulphur acid for adjusting pH value is 0.5; Extraordinarily go into S-WAT 13.5g by 1.3 of copper in the filter residue and cobalt element total mass; Reaction is 3 hours under 60 ℃ temperature, filters, and gets filter residue and filtrating respectively.The dried slag cobalt contents 0.17% of filter residue, copper content 0.18%.The total leaching yield 98.8% of cobalt, the total leaching yield 98.6% of copper.
Embodiment seven
A kind of method that from the copper cobalt concentrate, leaches copper and cobalt respectively may further comprise the steps:
(1) ammonia soaks: the equal granularity of making even is that (Cu:6.88% Co:8.01%), puts in the 400mL tap water in 1: 4 ratio of solid-to-liquid ratio, according to the Cu of copper cobalt concentrate: (NH for the ball milling copper cobalt concentrate 100g of 0.15mm
4)
2CO
3: NH
3Mol ratio be to add volatile salt 97g, strong aqua 83mL at 1: 10: 10, add VAL-DROP 3.5g, reaction is 1 hour under 60 ℃ temperature, filters, and gets filtrating and filter residue respectively.Copper in the ammonia leaching liquid is 12.4g/L, and cobalt contents 0.37g/L, iron level are 4.5mg/L, and the leaching yield of copper is 90.3%, cobalt leaching yield 2.3%, and iron, manganese leaching yield are 0.05%, filter residue is 86.5g.
(2) acidleach: getting filter residue, put in the 520mL tap water in 1: 6 ratio of solid-to-liquid ratio, is 1.5 with the salt acid for adjusting pH value; Extraordinarily go into S-WAT 11.9g by 1.4 of copper in the filter residue and cobalt element total mass; Reaction is 1 hour under 80 ℃ temperature, filters, and gets filter residue and filtrating respectively.The dried slag cobalt contents of filter residue is 0.12%, and copper content is 0.10%.The total leaching yield of cobalt is 98.8%, and the total leaching yield of copper is 98.9%.
Visible by embodiment one～seven, the copper in the step (1) in the gained filtrating is about 7～15g/L, and cobalt contents is 0.05～0.4g/L; Iron level is 0.1～7mg/L; The leaching yield of copper is 80%～99%, and the leaching yield of cobalt is 0.5%～3%, and iron, manganese leaching yield are 0.1%～0.5%.The content of the dried slag cobalt of gained filter residue is 0.08%～0.15% in the step (2), and copper content is 0.08%～0.16%.The total leaching yield of cobalt is 98.8%～99.5%, and the total leaching yield of copper is 98.6%～99.0%.
Embodiment eight simultaneous tests
Direct acidleach copper cobalt concentrate (metals such as cobalt, copper, iron and manganese are leached together).Get this leach liquor (composition: Co:20.1g/L, Cu:23.5g/L, Fe:5.6g/L, Mn:3.2g/L); With liquid caustic soda (concentration is 6mol/L) readjustment terminal point pH4.0, finally obtain removal of impurities liquid (composition: Co:19.5g/L, Cu:19.9g/L, Fe:0.38g/L, Mn:3.1g/L).Wherein, the rate of loss of cobalt is 3.5%, and the copper rate of loss is 16.2%, and the rate of removing of iron is 93.4%.By contrast; Soak-leach liquor (composition: Co:19.7g/L, Cu:2.8g/L, Fe:5.9g/L, Mn:3.5g/L) after the S-WAT acidleach by the inventive method ammonia; With liquid caustic soda (concentration is 6mol/L) readjustment terminal point pH4.0, finally obtain removal of impurities liquid (composition: Co:19.1g/L, Cu:2.4g/L, Fe:0.36g/L, Mn:3.4g/L).Wherein, the rate of loss of cobalt is 3.4%, and the loss of copper is 1.7%, the rate of removing 93.6% of iron.Copper loss is lost and has been reduced by 14.5%.
Embodiment nine
Ammonia soaks step and step of acid dipping as previously mentioned.
Get the ammonia leaching slag through the leach liquor (composition: Co:19.8g/L, Cu3.4g/L, Fe:7.5g/L, Mn:4.2g/L) after the acidleach; With liquid caustic soda (concentration is 10mol/L) readjustment terminal point pH4.0; Finally obtain removal of impurities liquid (composition: Co:18.7g/L, Cu:3.0g/L, Fe:0.072g/L, Mn:4.1g/L), with P204 extracting and separating cobalt, copper, P204 composition (volume ratio 1: 4=P204: sulfonated kerosene); Saponification degree 65%; Compare 1: 1 according to organic/feed liquid, through the extraction of 5 stage countercurrents, the raffinate that obtains (composition: Co:18.5g/L, Cu:3.4mg/L, Fe:2.1mg/L, Mn:4.2mg/L).With organicly comparing 6: 1 after the extraction according to organic/feed liquid; Washing sour H+ concentration is 0.5mol/L; The washing of three stage countercurrents obtains washings (composition: Co:13.2g/L, Cu:0.17g/L, Fe:0.11mg/L, Mn:0.08g/L), and washing water can be incorporated in the feed liquid.With organicly comparing 5: 1 according to organic/feed liquid after the washing, sour regurgitation H+ concentration is 3.0mol/L, four-stage counter-current back extraction, the strip liquor that obtains (composition: Co:0.02g/L, Cu:33.7g/L, Fe:0.82g/L, Mn:35.2g/L).
Claims (6)
1. a method that from the copper cobalt concentrate, leaches copper and cobalt respectively is characterized in that, may further comprise the steps:
(1) ammonia soaks: get the copper cobalt concentrate; Said copper cobalt concentrate mean particle size is 0.1～0.2mm; In solid-to-liquid ratio is that the ratio of 1: 2～6g/mL is put in the end water, and in said copper cobalt concentrate in the mol ratio of copper be that 1: 4～12 ratio adds volatile salt, and be that 1: 4～12 ratio feeds ammonia or ammoniacal liquor in mol ratio with said copper; Extraordinarily go into VAL-DROP by 0.3～0.5 of said copper quality subsequently; Under 30～60 ℃ temperature, reacted 1～3 hour, and filtered, get filtrating and filter residue respectively;
(2) acidleach: get said filter residue; In solid-to-liquid ratio is that the ratio of 1: 2～6g/mL is put in the end water; Adding sulfuric acid or salt acid for adjusting pH value is 0.5～1.5, extraordinarily goes into S-WAT by 1.2～1.5 of copper in the said filter residue and cobalt element total mass, under 60～80 ℃ temperature, reacts 1～3 hour; Filter, get filter residue and filtrating respectively.
2. the method for claim 1 is characterized in that, the mol ratio of the copper of copper cobalt concentrate, said volatile salt and said ammoniacal liquor is 1: 6～10: 6～10 described in the said step (1).
3. the method for claim 1 is characterized in that, the mol ratio of the copper of copper cobalt concentrate, said volatile salt and said ammoniacal liquor is 1: 9: 9 described in the said step (1).
4. the method for claim 1 is characterized in that, the mass ratio of the amount of VAL-DROP and said copper is 1: 2 described in the said step (1).
5. the method for claim 1 is characterized in that, described in the said step (2) in the amount of S-WAT and the said filter residue mass ratio of copper and cobalt element total mass be 3: 2.
6. the method for claim 1 is characterized in that, filtrating described in the said step (2) gets into the extraction line after iron ion and aluminum ion are removed in removal of impurities.
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| CN103272700B (en) * | 2013-06-07 | 2014-11-05 | 浙江华友钴业股份有限公司 | Method for flotation and recycling of copper and cobalt from copper-cobalt ore acid leached smelt slag |
| CN103480495B (en) * | 2013-09-27 | 2015-08-26 | 浙江华友钴业股份有限公司 | A kind of method selecting smelting to combine recovery copper cobalt from copper cobalt ore acidleach metallurgical slag |
| US9255308B2 (en) * | 2014-06-06 | 2016-02-09 | Soluciones Tecnológicas Mineras Coriolis Limitada | Methods of copper extraction |
| CN105316481A (en) * | 2014-11-12 | 2016-02-10 | 浙江华友钴业股份有限公司 | Crude cobalt salt leaching method |
| CN104726717B (en) * | 2015-04-01 | 2017-04-19 | 云南驰宏锌锗股份有限公司 | Method for recovering cobalt from inverse antimony purified cobalt residue |
| CN106222430B (en) * | 2016-08-04 | 2017-12-22 | 西北矿冶研究院 | A kind of hydrometallurgical recovery copper and cobalt method of copper cobalt slag |
| CN108728665A (en) * | 2018-05-04 | 2018-11-02 | 昆明理工大学 | A method of recycling copper from Water Quenching Slag |
| CN110564950B (en) * | 2019-08-26 | 2021-09-24 | 金川集团股份有限公司 | Refining method of copper-cobalt mixed ore |
| CN113528815B (en) * | 2021-07-28 | 2023-05-23 | 矿冶科技集团有限公司 | Method for recovering valuable metals from cobalt-manganese polymetallic oxide ore and application thereof |
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| US3907966A (en) * | 1972-06-28 | 1975-09-23 | Kennecott Copper Corp | Nickel extraction and stripping using oximes and ammoniacal carbonate solutions |
| CN1076494A (en) * | 1992-03-13 | 1993-09-22 | 北京矿冶研究总院 | Hydrometallurgical method for recovering copper from copper oxide ore |
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| US3907966A (en) * | 1972-06-28 | 1975-09-23 | Kennecott Copper Corp | Nickel extraction and stripping using oximes and ammoniacal carbonate solutions |
| CN1076494A (en) * | 1992-03-13 | 1993-09-22 | 北京矿冶研究总院 | Hydrometallurgical method for recovering copper from copper oxide ore |
| CN1966741A (en) * | 2006-10-27 | 2007-05-23 | 湖南瑞翔新材料有限公司 | Method for treating oxidized copper ore |
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