CN115927872A - Method for removing manganese and cobalt in zinc hydrometallurgy high-cobalt solution - Google Patents
Method for removing manganese and cobalt in zinc hydrometallurgy high-cobalt solution Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 238
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 238
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 215
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000011572 manganese Substances 0.000 title claims abstract description 102
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 101
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 100
- 239000011701 zinc Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 38
- 239000002893 slag Substances 0.000 claims abstract description 25
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 13
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910001437 manganese ion Inorganic materials 0.000 claims description 11
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- -1 iron ions Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229950011260 betanaphthol Drugs 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims 2
- 238000000746 purification Methods 0.000 description 25
- 239000012535 impurity Substances 0.000 description 11
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012629 purifying agent Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 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 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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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Abstract
The invention discloses a method for removing manganese and cobalt in a zinc hydrometallurgical high cobalt solution, which comprises the following steps: providing a zinc hydrometallurgy high cobalt solution; adding a demanganizing agent into the zinc hydrometallurgy high-cobalt solution, and carrying out an oxidation demanganizing reaction to obtain a demanganized solution; adding a cobalt removing agent into the solution after manganese removal, and carrying out oxidation cobalt removal reaction to obtain a cobalt removed solution; and carrying out solid-liquid separation on the solution after cobalt removal to obtain a cobalt manganese removal solution and cobalt manganese slag. According to the method, the manganese and cobalt are removed by adding the manganese removing agent and the cobalt removing agent into the zinc hydrometallurgy high cobalt solution to perform the reaction of removing manganese and cobalt through oxidation, so that the finally obtained manganese and cobalt removing solution is low in manganese and cobalt content.
Description
Technical Field
The invention relates to the field of nonferrous metallurgy, in particular to a method for removing manganese and cobalt in a zinc hydrometallurgy high-cobalt solution.
Background
Cobalt is a harmful impurity element in the zinc hydrometallurgy process, and the electrolysis can be carried out only when the cobalt is removed to reach the qualified standard before entering an electrolysis system. In the purification and cobalt removal process, in order to ensure the qualification rate of the liquid after cobalt removal, part of cobalt is usually removed in one section of purification, the removed part of cobalt enters the next process along with one section of purification slag, and is subjected to leaching-replacement to obtain copper-rich slag, sponge cadmium and high-cobalt solution, the copper-rich slag and the sponge cadmium are sold as products, the high-cobalt solution contains valuable metal zinc and needs to be returned to a purification system for reprocessing and recovering the zinc, and the solution returned to the purification system needs to be subjected to cobalt removal because the impurity cobalt content is high, so as to ensure the stable operation of purification production. The existing cobalt removing method of the high cobalt solution mainly comprises a zinc powder replacement method, a xanthate purification cobalt removing method, a beta-naphthol purification cobalt removing method, a novel purifying agent cobalt removing method and the like, and the methods have the defects of large zinc powder consumption, harmful impurity organic matters brought in and the like.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for removing manganese and cobalt in a zinc hydrometallurgy high cobalt solution, and aims to solve the problems that harmful impurities and organic matters are brought in the existing cobalt removal method for the high cobalt solution, and the cost is high.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for removing manganese and cobalt in a zinc hydrometallurgy high-cobalt solution comprises the following steps:
providing a zinc hydrometallurgy high cobalt solution;
adding a demanganizing agent into the zinc hydrometallurgy high-cobalt solution, and carrying out oxidation demanganization reaction to obtain a demanganized solution;
adding a cobalt removing agent into the solution after manganese removal, and performing an oxidation cobalt removing reaction to obtain a solution after cobalt removal;
and carrying out solid-liquid separation on the solution after cobalt removal to obtain a cobalt manganese removal solution and cobalt manganese slag.
The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution comprises the steps of removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution, wherein the zinc hydrometallurgical high cobalt solution contains zinc ions, cobalt ions, manganese ions, cadmium ions and iron ions.
The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution comprises the step of selecting a manganese removing agent from O 3 And one or two of caro acid.
The method for removing manganese and cobalt in the zinc hydrometallurgy high cobalt solution comprises the following steps of:
adding a manganese removing agent into the zinc hydrometallurgy high cobalt solution, adding a NaOH solution into the zinc hydrometallurgy high cobalt solution to adjust the pH value of the zinc hydrometallurgy high cobalt solution to 3.5-4.0, and carrying out oxidation manganese removal reaction; wherein the temperature of the oxidation demanganization reaction is 20-30 ℃, and the time of the oxidation demanganization reaction is 0.5-1h.
The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution comprises the step of selecting a cobalt removing agent from O 3 One or more of ammonium sulfate, zinc powder-antimony salt, carlo acid and beta-naphthol.
The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution comprises the following steps of: 1.
the method for removing manganese and cobalt in the zinc hydrometallurgy high-cobalt solution comprises the following steps of:
adding a cobalt removing agent into the solution after manganese removal, adding a NaOH solution into the solution after manganese removal to adjust the pH value of the solution after manganese removal to 3.5-4.0, and performing oxidation cobalt removal reaction; wherein the temperature of the oxidation cobalt-removing reaction is 20-30 ℃, and the time of the oxidation cobalt-removing reaction is 0.5-2h.
The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution is characterized in that the concentration of manganese ions in the solution after manganese removal is less than 1g/L.
The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution is characterized in that the concentration of cobalt ions in the solution after cobalt removal is less than 100mg/L.
The method for removing manganese and cobalt in the zinc hydrometallurgy high-cobalt solution comprises the following steps after the step of obtaining the solution for removing manganese and cobalt and the manganese and cobalt slag:
and returning the manganese-cobalt-removed solution to a zinc hydrometallurgy system, and conveying the manganese-cobalt slag to a volatilization kiln workshop to recover metal zinc.
Has the advantages that: the invention discloses a method for removing manganese and cobalt in a zinc hydrometallurgical high cobalt solution, which is characterized in that a manganese removing agent and a cobalt removing agent are added into the zinc hydrometallurgical high cobalt solution to generate the reaction of removing manganese and cobalt through oxidation, so that the removal of manganese and cobalt in the zinc hydrometallurgical high cobalt solution is realized, the finally obtained manganese and cobalt content in the cobalt solution is lower, the consumption of zinc powder can be avoided by adopting the method, new harmful impurity organic matters can not be brought in, the purification of the zinc hydrometallurgical high cobalt solution is realized cleanly and efficiently, and the phenomenon that the cobalt content in the zinc hydrometallurgical high cobalt solution is higher and the production fluctuation is caused when the zinc hydrometallurgical high cobalt solution enters a purification system is avoided.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of the method for removing manganese and cobalt in a zinc hydrometallurgical high cobalt solution provided by the invention.
Detailed Description
The invention provides a method for removing manganese and cobalt in a zinc hydrometallurgical high cobalt solution, and the method is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the zinc hydrometallurgy process, cobalt is a harmful impurity element, and before entering an electrolysis system, the cobalt is removed to reach a qualified standard to carry out electrolysis. In the purification and cobalt removal process, in order to ensure the qualification rate of the liquid after cobalt removal, part of cobalt is usually removed in one section of purification, the removed part of cobalt enters the next process along with one section of purification slag, and is subjected to leaching-replacement to obtain copper-rich slag, sponge cadmium and high-cobalt solution, the copper-rich slag and the sponge cadmium are sold as products, the high-cobalt solution contains valuable metal zinc and returns to a purification system for reprocessing and zinc recovery, and the solution returned to the purification system needs to be subjected to cobalt removal because the impurity cobalt content is high, so as to ensure the stable operation of purification production.
However, in the prior art, the methods for removing cobalt from a high-cobalt solution mainly include a zinc powder replacement method, a xanthate purification cobalt removal method, a beta-naphthol purification cobalt removal method, a novel purifying agent cobalt removal method and the like, and all of the methods have the disadvantages of large consumption of zinc powder, introduction of harmful impurity organic matters and the like.
Based on the above, the invention provides a method for removing manganese and cobalt in zinc hydrometallurgy high cobalt solution, referring to fig. 1, which comprises the following steps:
s10, providing a zinc hydrometallurgy high-cobalt solution;
s20, adding a demanganizing agent into the zinc hydrometallurgical high-cobalt solution, and performing an oxidation demanganizing reaction to obtain a demanganized solution;
s30, adding a cobalt removing agent into the solution after manganese removal, and carrying out oxidation cobalt removing reaction to obtain a solution after cobalt removal;
s40, carrying out solid-liquid separation on the cobalt-removed solution to obtain a cobalt-manganese-removed solution and cobalt-manganese slag.
Specifically, the method disclosed by the invention has the advantages that the manganese and cobalt in the zinc hydrometallurgical high cobalt solution are removed by adding the manganese removing agent and the cobalt removing agent into the zinc hydrometallurgical high cobalt solution to perform the reaction of removing manganese and cobalt through oxidation, so that the finally obtained manganese and cobalt removing solution is low in manganese and cobalt content.
In some embodiments, the zinc hydrometallurgical high cobalt solution contains zinc ions, cobalt ions, manganese ions, cadmium ions and iron ions, wherein the cobalt ion concentration in the zinc hydrometallurgical high cobalt solution is 200-900mg/L, and the manganese ion concentration is 1200-3600mg/L.
Specifically, the zinc hydrometallurgy solution in the invention is produced in a cadmium recovery process of zinc hydrometallurgy, a part of cobalt in the zinc hydrometallurgy solution is removed in a first section of purification process, the removed cobalt enters the next process along with a section of purification slag, and copper-rich slag, sponge cadmium and high cobalt solution are obtained after leaching-replacement, wherein the high cobalt solution is the zinc hydrometallurgy high cobalt solution in the invention, so that the zinc hydrometallurgy high cobalt solution contains zinc ions, cobalt ions, manganese ions, cadmium ions and iron ions.
In some embodiments, the demanganizing agent is selected from O 3 And one or two of caro acid.
Specifically, the demanganizing agent is a substance with high oxidizability, and can quickly oxidize soluble divalent manganese in the zinc hydrometallurgy high-cobalt solution into tetravalent insoluble manganese, oxidize the soluble divalent manganese into trivalent insoluble iron, and simultaneously remove iron ions and manganese ions in the zinc hydrometallurgy high-cobalt solution.
In some embodiments, the step of adding a demanganizing agent to the zinc hydrometallurgical high cobalt solution to perform an oxidative demanganization reaction comprises the steps of:
adding a manganese removing agent into the zinc hydrometallurgy high cobalt solution, adding a NaOH solution into the zinc hydrometallurgy high cobalt solution to adjust the pH value of the zinc hydrometallurgy high cobalt solution to 3.5-4.0, and carrying out an oxidation manganese removal reaction; wherein the temperature of the oxidation demanganization reaction is 20-30 ℃, the time of the oxidation demanganization reaction is 0.5-1h, and manganese in the solution can be efficiently removed under the reaction condition.
In some embodiments, the cobalt removal agent is selected from peroxy 3 One or more of ammonium sulfate, zinc powder-antimony salt, carlo acid and beta-naphthol.
Specifically, the cobalt removing agent is a substance with high oxidizability, and can quickly oxidize soluble divalent cobalt in the solution after manganese removal into trivalent insoluble cobalt, so that cobalt ions in the zinc hydrometallurgy high-cobalt solution can be removed.
In some embodiments, the mass ratio of the cobalt removal agent to the cobalt ions in the post-manganese removal solution is (10-30): 1, the required addition amount of the cobalt removing agent can be calculated by detecting the cobalt content in the cobalt-containing solution.
In some embodiments, the step of adding a cobalt removal agent to the solution after manganese removal to perform an oxidation cobalt removal reaction includes the steps of:
adding a cobalt removing agent into the solution after manganese removal, adding a NaOH solution into the solution after manganese removal to adjust the pH value of the solution after manganese removal to 3.5-4.0, and performing oxidation cobalt removal reaction; wherein the temperature of the oxidation cobalt-removing reaction is 20-30 ℃, the time of the oxidation cobalt-removing reaction is 0.5-2h, and the cobalt in the solution can be efficiently removed under the reaction condition.
The manganese removal reaction and the cobalt removal reaction are carried out at normal temperature by the solution system to obtain manganese-cobalt slag and the manganese-cobalt removal solution, and the reaction system does not need to be heated, so that steam is saved. Meanwhile, the demanganizing agent and the demanganizing agent are used as the oxidant to carry out the oxidation reactions of demanganizing and demanganizing, so that other harmful impurities are not brought into the system, and the system is not influenced.
In some embodiments, the concentration of manganese ions in the solution after demanganization is less than 1g/L.
In some embodiments, the concentration of cobalt ions in the solution after cobalt removal is less than 100mg/L.
In some embodiments, after the step of obtaining the solution for removing manganese and cobalt and the manganese and cobalt slag, the method further comprises the steps of:
and returning the manganese-cobalt-removed solution to a zinc hydrometallurgy system, and conveying the manganese-cobalt slag to a volatilization kiln workshop to recover metal zinc.
In some preferred embodiments, O is selected as the manganese remover and the cobalt remover 3 Using a cleaning raw material O 3 Carrying out oxidation cobalt precipitation treatment on the zinc hydrometallurgy high-cobalt solution to reduce the cobalt content in the solution, so as to obtain a manganese-cobalt-removed solution and manganese-cobalt slag, conveying the manganese-cobalt-removed solution to a zinc smelting system for recovering zinc, and conveying the manganese-cobalt slag to a volatilization kiln for recovering zinc. The cobalt content in the manganese-cobalt-removing solution is low, and the solution enters a purification system as a purification pre-solution, so that the problems that the cobalt content in a zinc hydrometallurgy high-cobalt solution (the purification pre-solution) is high, the production fluctuation is caused when the solution enters the purification process, and the unit consumption of zinc powder is increased in the prior art can be solved; by using O 3 The clean gas removes the cobalt-containing solution, so that the problems of low cobalt removal efficiency, generation of a large amount of zinc-containing purification slag and introduction of new impurities into the system in the prior art can be solved.
O 3 The invention utilizes the strong oxidizing property of ozone to oxidize manganese ions, iron ions and cobalt ions in the solution to remove the manganese ions, iron ions and cobalt ions by hydrolysis and precipitation, can avoid secondary pollution caused by adding the traditional chemical precipitator by utilizing the ozone, and simultaneously can be used for cleaning and developing the environment-friendly high-efficiency oxidizing agentThe process product of ozone oxygen preparation is O 2 Is a clean and high-efficiency process, and O is selected 3 As cobalt removal agent, cobalt is precipitated out in the form of CoOOH.
By the use of O 3 When the catalyst is used as a manganese remover and a cobalt remover, the reaction in the solution mainly comprises the following steps:
Mn 2+ +O 3 +H 2 O→MnO 2 +O 2 +H +
Fe 2+ +O 3 +H 2 O→FeOOH/Fe(OH) 3 +O 2 +H +
2Co 2+ +O 3 +H 2 O→2CoOOH+4H + +1/2O 2
concretely, adding a zinc hydrometallurgy high cobalt solution into a reaction tank, and introducing O 3 Removing manganese by oxidation for 0.5-1h, adjusting the pH value of the solution system to 3.5-4.0, and continuously introducing O after the reaction 3 Performing oxidation cobalt removal reaction for 1-2h, adjusting the pH value of a solution system to 3.5-4.0, performing solid-liquid separation after the reaction is finished to obtain manganese-cobalt slag and a manganese-cobalt removal solution, wherein the manganese-cobalt slag is sent to a volatilization kiln to recover valuable metal zinc, and the manganese-cobalt removal solution enters a zinc smelting system to recover zinc.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is clear that the described embodiments are only a part of the embodiments of the invention, not all embodiments, merely intended to illustrate the invention and in no way limit it. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
2L of zinc hydrometallurgy high cobalt solution (containing 1.698g of cobalt and 3.62g of manganese) is added into a reaction tank, and O is introduced at normal temperature 3 Adjusting the pH value of the system to 3.0 by adding NaOH, controlling the reaction time to be 1h, and continuously introducing O after the reaction is finished 3 And adjusting the pH value of the system to 3.0 by adding NaOH, controlling the reaction time to be 1h, and obtaining the solution after cobalt removal after the reaction is finished. Filtering the solution after cobalt removalThe obtained solution for removing manganese and cobalt contains 0.1g/L of cobalt and 0.49g/L of manganese.
Example 2
2L of zinc hydrometallurgy high cobalt solution (containing 1.698g of cobalt and 3.62g of manganese) is added into a reaction tank, and O is introduced at normal temperature 3 Adding NaOH to adjust the pH value of the system to 3.5, controlling the reaction time to be 1h, and continuously introducing O after the reaction is finished 3 And adjusting the pH value of the system to 3.5 by adding NaOH, controlling the reaction time to be 1h, and obtaining the solution after cobalt removal after the reaction is finished. The cobalt-removing solution obtained after cobalt removal is filtered contains 0.052g/L of cobalt and 0.3g/L of manganese.
Example 3
2L of zinc hydrometallurgy high cobalt solution (containing 1.698g of cobalt and 3.62g of manganese) is added into a reaction tank, and O is introduced at normal temperature 3 Adjusting the pH value of the system to 4.0 by adding NaOH, controlling the reaction time to be 1h, and continuously introducing O after the reaction is finished 3 And adjusting the pH value of the system to 4.0 by adding NaOH, controlling the reaction time to be 1h, and obtaining the solution after cobalt removal after the reaction is finished. The cobalt-removing solution obtained after cobalt removal is filtered contains 0.03g/L of cobalt and 0.1g/L of manganese.
As can be seen from examples 1-3, the pH value of the solution has a large effect on cobalt and manganese removal at normal temperature, and when the pH value of the solution is greater than 3.5, the impurity content of the cobalt-removed solution is low, so that the pH value of the reaction solution system is preferably controlled to be 3.5.
In summary, the invention discloses a method for removing manganese and cobalt in zinc hydrometallurgical high cobalt solution, which comprises the following steps: providing a zinc hydrometallurgy high cobalt solution; adding a demanganizing agent into the zinc hydrometallurgy high-cobalt solution, and carrying out an oxidation demanganizing reaction to obtain a demanganized solution; adding a cobalt removing agent into the solution after manganese removal, and carrying out oxidation cobalt removal reaction to obtain a solution after cobalt removal; and carrying out solid-liquid separation on the cobalt-removed solution to obtain a manganese-cobalt-removed solution and manganese-cobalt slag. According to the method, the manganese and cobalt in the zinc hydrometallurgical high cobalt solution are removed by adding the manganese removing agent and the cobalt removing agent into the zinc hydrometallurgical high cobalt solution to perform the reaction of removing manganese and cobalt through oxidation, so that the finally obtained manganese and cobalt removing solution is low in manganese and cobalt content.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for removing manganese and cobalt in a zinc hydrometallurgy high-cobalt solution is characterized by comprising the following steps:
providing a zinc hydrometallurgy high cobalt solution;
adding a demanganizing agent into the zinc hydrometallurgy high-cobalt solution, and carrying out an oxidation demanganizing reaction to obtain a demanganized solution;
adding a cobalt removing agent into the solution after manganese removal, and performing an oxidation cobalt removing reaction to obtain a solution after cobalt removal;
and carrying out solid-liquid separation on the solution after cobalt removal to obtain a cobalt manganese removal solution and cobalt manganese slag.
2. The method for removing manganese and cobalt in the zinc hydrometallurgical cobaltous solution according to claim 1, wherein the zinc hydrometallurgical cobaltous solution contains zinc ions, cobalt ions, manganese ions, cadmium ions and iron ions.
3. The method for removing manganese and cobalt in zinc hydrometallurgical high cobalt solution according to claim 1, wherein the demanganizing agent is selected from O 3 And one or two of caro acid.
4. The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution according to claim 1, wherein the step of adding a manganese removing agent into the zinc hydrometallurgical high cobalt solution to perform an oxidation manganese removal reaction comprises the steps of:
adding a manganese removing agent into the zinc hydrometallurgy high cobalt solution, adding a NaOH solution into the zinc hydrometallurgy high cobalt solution to adjust the pH value of the zinc hydrometallurgy high cobalt solution to 3.5-4.0, and carrying out oxidation manganese removal reaction; wherein the temperature of the oxidation demanganization reaction is 20-30 ℃, and the time of the oxidation demanganization reaction is 0.5-1h.
5. The method for removing manganese and cobalt in zinc hydrometallurgical high cobalt solution according to claim 1, wherein the cobalt removing agent is selected from peroxy O 3 One or more of ammonium sulfate, zinc powder-antimony salt, carlo acid and beta-naphthol.
6. The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution according to claim 1, wherein the mass ratio of the cobalt removing agent to the cobalt ions in the solution after manganese removal is (10-30): 1.
7. the method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution according to claim 1, wherein the step of adding a cobalt removal agent to the solution after manganese removal to perform an oxidation cobalt removal reaction comprises the steps of:
adding a cobalt removing agent into the solution after manganese removal, adding a NaOH solution into the solution after manganese removal to adjust the pH value of the solution after manganese removal to 3.5-4.0, and performing oxidation cobalt removal reaction; wherein the temperature of the oxidation cobalt-removing reaction is 20-30 ℃, and the time of the oxidation cobalt-removing reaction is 0.5-2h.
8. The method for removing manganese and cobalt in a zinc-removing hydrometallurgical high cobalt solution according to claim 1, wherein the concentration of manganese ions in the solution after manganese removal is less than 1g/L.
9. The method for removing manganese and cobalt in the zinc-hydrometallurgical high cobalt solution according to claim 1, wherein the concentration of cobalt ions in the solution after cobalt removal is less than 100mg/L.
10. The method for removing manganese and cobalt in the zinc hydrometallurgical high cobalt solution according to claim 1, wherein after the step of obtaining the solution for removing manganese and cobalt and the manganese and cobalt slag, the method further comprises the steps of:
and returning the manganese-cobalt-removed solution to a zinc hydrometallurgy system, and conveying the manganese-cobalt slag to a volatilization kiln workshop to recover metal zinc.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103725890A (en) * | 2014-01-07 | 2014-04-16 | 中南大学 | Method for recycling valuable metals step by step from zinc-manganese-cobalt-rich slag in multiplex control manner |
| CN113881857A (en) * | 2021-09-09 | 2022-01-04 | 云南云铜锌业股份有限公司 | Method for treating cobalt-containing solution produced in wet zinc smelting cadmium recovery process |
| CN115011812A (en) * | 2022-03-23 | 2022-09-06 | 安徽铜冠有色金属（池州）有限责任公司 | Novel process for purifying supernatant of neutral leaching of zinc hydrometallurgy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725890A (en) * | 2014-01-07 | 2014-04-16 | 中南大学 | Method for recycling valuable metals step by step from zinc-manganese-cobalt-rich slag in multiplex control manner |
| CN113881857A (en) * | 2021-09-09 | 2022-01-04 | 云南云铜锌业股份有限公司 | Method for treating cobalt-containing solution produced in wet zinc smelting cadmium recovery process |
| CN115011812A (en) * | 2022-03-23 | 2022-09-06 | 安徽铜冠有色金属（池州）有限责任公司 | Novel process for purifying supernatant of neutral leaching of zinc hydrometallurgy |
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